Activation volume of selected liquid crystals in the density scaling regime

In this paper, we demonstrate and thoroughly analyze the activation volumetric properties of selected liquid crystals in the nematic and crystalline E phases in comparison with those reported for glass-forming liquids. In the analysis, we have employed and evaluated two entropic models (based on either total or configurational entropies) to describe the longitudinal relaxation times of the liquid crystals in the density scaling regime. In this study, we have also exploited two equations of state: volumetric and activation volumetric ones. As a result, we have established that the activation volumetric properties of the selected liquid crystals are quite opposite to such typical properties of glass-forming materials, i.e., the activation volume decreases and the isothermal bulk modulus increases when a liquid crystal is isothermally compressed. Using the model based on the configurational entropy, we suggest that the increasing pressure dependences of the activation volume in isothermal conditions and the negative curvature of the pressure dependences of isothermal longitudinal relaxation times can be related to the formation of antiparallel doublets in the examined liquid crystals. A similar pressure effect on relaxation dynamics may be also observed for other material groups in case of systems, the molecules of which form some supramolecular structures

A pathway towards proper modeling of physical properties

Theoretical concepts in condensed matter physics are typically verified and also developed by exploiting computer simulations mostly in simple models. Predictions based on these usually isotropic models are often at odds with measurement results obtained for real materials. On the other hand, all-atom simulations are complex and time-consuming. In this paper, we formulate a new strategy for effective molecular modelling, which properly reflects properties of real particles by using quasi-real molecules of simple but anisotropic architecture and identifying the applicable range of intermolecular interactions for a given physical process or quantity. As a demonstration of our method capabilities, we solve an intriguing problem within the density scaling idea that has attracted attention in recent decades due to its hallmarks of universality. It demonstrates that the new strategy for molecular modelling opens broad perspectives for simulation and theoretical research, for example, into unifying concepts in the glass transition physics

Observation of highly decoupled conductivity in protic ionic conductors

YesIonic liquids (ILs) are key materials for the development of a wide range of emerging technologies. Protic ionic liquids, an important class of ILs, have long been envisioned as promising anhydrous electrolytes for fuel cells. It is well known that in comparison to all other cations, protons exhibit abnormally high conductivity in water. Such superprotonic dynamics was expected in protic ionic conductors as well. However, many years of extensive studies led to the disappointing conclusion that this is not the case and most protic ionic liquids display subionic behavior. Therefore, the relatively low conductivity seems to be the main obstacle for the application of protic ionic liquids in fuel cells. Using dielectric spectroscopy, herein we report the observation of highly decoupled conductivity in a newly synthesized protic ionic conductor. We show that its proton transport is strongly decoupled from the structural relaxation, in terms of both temperature dependence and characteristic rates. This finding offers a fresh look on the charge transport mechanism in PILs and also provides new ideas for design of anhydrous materials with exceptionally high proton conductivity.National Science Centre within the framework of the Opus project (Grant No. DEC 2011/03/B/ST3/02072). Financial assistance from FNP START. The LDRD Program of ORNL, managed by UT-Battelle, LLC, for the U.S. DOE. Support from the NSF under grant CHE-1213444

Rank Maximal Matchings -- Structure and Algorithms

Let G = (A U P, E) be a bipartite graph where A denotes a set of agents, P denotes a set of posts and ranks on the edges denote preferences of the agents over posts. A matching M in G is rank-maximal if it matches the maximum number of applicants to their top-rank post, subject to this, the maximum number of applicants to their second rank post and so on. In this paper, we develop a switching graph characterization of rank-maximal matchings, which is a useful tool that encodes all rank-maximal matchings in an instance. The characterization leads to simple and efficient algorithms for several interesting problems. In particular, we give an efficient algorithm to compute the set of rank-maximal pairs in an instance. We show that the problem of counting the number of rank-maximal matchings is #P-Complete and also give an FPRAS for the problem. Finally, we consider the problem of deciding whether a rank-maximal matching is popular among all the rank-maximal matchings in a given instance, and give an efficient algorithm for the problem

Self-assembled carrageenan/protamine polyelectrolyte nanoplexes-Investigation of critical parameters governing their formation and characteristics

YesThe aim of this work was to investigate the feasibility of cross-linker free polyelectrolyte complex formation at the nanoscale between carrageenan (CAR) and protamine (PROT). The properties of CAR/PROT nanoparticles (NPs) were dependent on the carrageenan type: kappa (KC), iota (IC) and lambda (LC), concentration of components, addition of divalent cations, weight mixing ratio (WMR) of constituents and mode of component addition. In the case of 0.1% w/v solutions, IC-based NPs had the smallest particle sizes (100-150nm) and low polydispersity indices (0.1-0.4). A decrease in the solution concentration from 0.1% to 0.05% w/v enabled the formation of KC/PROT NPs. All carrageenans exhibited the ability to form NPs with surface charge ranging from -190 to 40mV. The inclusion of divalent cations caused an increase in the particle size and zeta potential. Infrared analysis confirmed the presence of a complex between CAR and PROT and showed that IC chains undergo structural changes when forming NPs. Colloidal stability of NPs was related to the initial surface charge of particles and was time- and pH-dependent. IC was found to be the most suitable type of CAR when forming nanoplexes with PROT

Self-assembled carrageenan/protamine polyelectrolyte nanoplexes-Investigation of critical parameters governing their formation and characteristics

YesThe aim of this work was to investigate the feasibility of cross-linker free polyelectrolyte complex formation at the nanoscale between carrageenan (CAR) and protamine (PROT). The properties of CAR/PROT nanoparticles (NPs) were dependent on the carrageenan type: kappa (KC), iota (IC) and lambda (LC), concentration of components, addition of divalent cations, weight mixing ratio (WMR) of constituents and mode of component addition. In the case of 0.1% w/v solutions, IC-based NPs had the smallest particle sizes (100-150nm) and low polydispersity indices (0.1-0.4). A decrease in the solution concentration from 0.1% to 0.05% w/v enabled the formation of KC/PROT NPs. All carrageenans exhibited the ability to form NPs with surface charge ranging from -190 to 40mV. The inclusion of divalent cations caused an increase in the particle size and zeta potential. Infrared analysis confirmed the presence of a complex between CAR and PROT and showed that IC chains undergo structural changes when forming NPs. Colloidal stability of NPs was related to the initial surface charge of particles and was time- and pH-dependent. IC was found to be the most suitable type of CAR when forming nanoplexes with PROT

Molecular dynamics and physical stability of amorphous nimesulide drug and its binary drug-polymer systems

yesIn this paper we study the effectiveness of three well known polymers: inulin, Soluplus and PVP in stabilizing amorphous form of nimesulide (NMS) drug. The re-crystallization tendency of pure drug as well as measured drug-polymer systems were examined at isothermal conditions by using broadband dielectric spectroscopy (BDS), and at non-isothermal conditions by differential scanning calorimetry (DSC). Our investigation has shown that the crystallization half-life time of pure NMS at 328 K is equal to 33 minutes. We found that this time can be prolonged to 40 years after adding to NMS 20% of PVP polymer. This polymer proved to be the best NMS’s stabilizer, while the worst stabilization effect was found after adding the inulin to NMS. Additionally, our DSC, BDS and FTIR studies indicate that for suppression of NMS’s re-crystallization in NMS-PVP system, the two mechanisms are responsible: the polymeric steric hindrances as well as the antiplastization effect excerted by the excipient.The authors J.K., Z.W., K.G. and M.P., are grateful for the financial support received within the Project No. 2015/16/W/NZ7/00404 (SYMFONIA 3) from the National Science Centre, Poland. H.M. and L.T. are supported by Science Foundation Ireland under grant No. 12/RC/2275 (Synthesis and Solid State Pharmaceuticals Centre)

Steering cell migration by alternating blebs and actin-rich protrusions

Background High directional persistence is often assumed to enhance the efficiency of chemotactic migration. Yet, cells in vivo usually display meandering trajectories with relatively low directional persistence, and the control and function of directional persistence during cell migration in three-dimensional environments are poorly understood. Results Here, we use mesendoderm progenitors migrating during zebrafish gastrulation as a model system to investigate the control of directional persistence during migration in vivo. We show that progenitor cells alternate persistent run phases with tumble phases that result in cell reorientation. Runs are characterized by the formation of directed actin-rich protrusions and tumbles by enhanced blebbing. Increasing the proportion of actin-rich protrusions or blebs leads to longer or shorter run phases, respectively. Importantly, both reducing and increasing run phases result in larger spatial dispersion of the cells, indicative of reduced migration precision. A physical model quantitatively recapitulating the migratory behavior of mesendoderm progenitors indicates that the ratio of tumbling to run times, and thus the specific degree of directional persistence of migration, are critical for optimizing migration precision. Conclusions Together, our experiments and model provide mechanistic insight into the control of migration directionality for cells moving in three-dimensional environments that combine different protrusion types, whereby the proportion of blebs to actin-rich protrusions determines the directional persistence and precision of movement by regulating the ratio of tumbling to run times

Manipulation Strategies for the Rank Maximal Matching Problem

We consider manipulation strategies for the rank-maximal matching problem. In the rank-maximal matching problem we are given a bipartite graph $G = (A \cup P, E)$ such that $A$ denotes a set of applicants and $P$ a set of posts. Each applicant $a \in A$ has a preference list over the set of his neighbours in $G$, possibly involving ties. Preference lists are represented by ranks on the edges - an edge $(a,p)$ has rank $i$, denoted as $rank(a,p)=i$, if post $p$ belongs to one of $a$'s $i$-th choices. A rank-maximal matching is one in which the maximum number of applicants is matched to their rank one posts and subject to this condition, the maximum number of applicants is matched to their rank two posts, and so on. A rank-maximal matching can be computed in $O(\min(c \sqrt{n},n) m)$ time, where $n$ denotes the number of applicants, $m$ the number of edges and $c$ the maximum rank of an edge in an optimal solution. A central authority matches applicants to posts. It does so using one of the rank-maximal matchings. Since there may be more than one rank- maximal matching of $G$, we assume that the central authority chooses any one of them randomly. Let $a_1$ be a manipulative applicant, who knows the preference lists of all the other applicants and wants to falsify his preference list so that he has a chance of getting better posts than if he were truthful. In the first problem addressed in this paper the manipulative applicant $a_1$ wants to ensure that he is never matched to any post worse than the most preferred among those of rank greater than one and obtainable when he is truthful. In the second problem the manipulator wants to construct such a preference list that the worst post he can become matched to by the central authority is best possible or in other words, $a_1$ wants to minimize the maximal rank of a post he can become matched to

Impact of alternative solid state forms and specific surface area of high-dose, hydrophilic active pharmaceutical ingredients on tabletability

YesIn order to investigate the effect of using different solid state forms and specific surface area (TBET) of active pharmaceutical ingredients on tabletability and dissolution performance, the mono- and dihydrated crystalline forms of chlorothiazide sodium and chlorothiazide potassium (CTZK) salts were compared to alternative anhydrous and amorphous forms, as well as to amorphous microparticles of chlorothiazide sodium and potassium which were produced by spray drying and had a large specific surface area. The tablet hardness and tensile strength, porosity, and specific surface area of single-component, convex tablets prepared at different compression pressures were characterized. Results confirmed the complexity of the compressibility mechanisms. In general it may be concluded that factors such as solid-state form (crystalline vs amorphous), type of hydration (presence of interstitial molecules of water, dehydrates), or specific surface area of the material have a direct impact on the tabletability of the powder. It was observed that, for powders of the same solid state form, those with a larger specific surface area compacted well, and better than powders of a lower surface area, even at relatively low compression pressures. Compacts prepared at lower compression pressures from high surface area porous microparticles presented the shortest times to dissolve, when compared with compacts made of equivalent materials, which had to be compressed at higher compression pressures in order to obtain satisfactory compacts. Therefore, materials composed of nanoparticulate microparticles (NPMPs) may be considered as suitable for direct compaction and possibly for inclusion in tablet formulations as bulking agents, APIs, carriers, or binders due to their good compactibility performanceSolid State Pharmaceutical Cluster (SSPC), supported by Science Foundation Ireland under Grant No. 07/SRC/B1158