(Nano)Granules-Involving Aggregation at a Passage to the Nanoscale as Viewed in Terms of a Diffusive Heisenberg Relation.

We are looking at an aggregation of matter into granules. Diffusion plays a pivotal role here. When going down to the nanometer scale (the so-called nanoscale quantum-size effect limit), quantum mechanics, and the Heisenberg uncertainty relation, may take over the role of classical diffusion, as viewed typically in the mesoscopic/stochastic limit. A d-dimensional entropy-production aggregation of the granules-involving matter in the granule-size space is considered in terms of a (sub)diffusive realization. It turns out that when taking a full d-dimensional pathway of the aggregation toward the nanoscale, one is capable of disclosing a Heisenberg-type (diffusional) relation, setting up an upper uncertainty bound for the (sub)diffusive, very slow granules-including environment that, within the granule-size analogy invoked, matches the quantum limit of h/2πµ (µ-average mass of a granule; h-the Planck's constant) for the diffusion coefficient of the aggregation, first proposed by Fürth in 1933 and qualitatively foreseen by Schrödinger some years before, with both in the context of a diffusing particle. The classical quantum passage uncovered here, also termed insightfully as the quantum-size effect (as borrowed from the quantum dots' parlance), works properly for the three-dimensional (d = 3) case, making use of a substantial physical fact that the (nano)granules interact readily via their surfaces with the also-granular surroundings in which they are immersed. This natural observation is embodied in the basic averaging construction of the diffusion coefficient of the entropy-productive (nano)aggregation of interest.

Dissipative, Entropy Production Systems across Condensed Matter and Interdisciplinary Classical vs. Quantum Physics.

This Special Issue collected ten papers addressing a range of topics in condensed matter and interdisciplinary classical vs [...].

Spherulites: How Do They Emerge at an Onset of Nonequilibrium Kinetic-Thermodynamic and Structural Singularity Addressing Conditions?

This communication addresses the question of the far-from-equilibrium growth of spherulites with different growing modes. The growth occurs in defects containing and condensed matter addressing environments of (bio)polymeric and biominerals involving outcomes. It turns out that it is possible to anticipate that, according to our considerations, there is a chance of spherulites' emergence prior to a pure diffusion-controlled (poly)crystal growth. Specifically, we have shown that the emergence factors of the two different evolution types of spherulitic growth modes, namely, diffusion-controlled growth and mass convection-controlled growth, appear. As named by us, the unimodal crystalline Mullins-Sekerka type mode of growth, characteristic of local curvatures' presence, seems to be more entropy-productive in its emerging (structural) nature than the so-named bimodal or Goldenfeld type mode of growth. In the latter, the local curvatures do not play any crucial roles. In turn, a liaison of amorphous and crystalline phases makes the system far better compromised to the thermodynamic-kinetic conditions it actually, and concurrently, follows. The dimensionless character of the modeling suggests that the system does not directly depend upon experimental details, manifesting somehow its quasi-universal, i.e., scaling addressing character.

Effect of Chitosan Deacetylation on Its Affinity to Type III Collagen: A Molecular Dynamics Study.

The ability to form strong intermolecular interactions by linear glucosamine polysaccharides with collagen is strictly related to their nonlinear dynamic behavior and hence bio-lubricating features. Type III collagen plays a crucial role in tissue regeneration, and its presence in the articular cartilage affects its bio-technical features. In this study, the molecular dynamics methodology was applied to evaluate the effect of deacetylation degree on the chitosan affinity to type III collagen. The computational procedure employed docking and geometry optimizations of different chitosan structures characterized by randomly distributed deacetylated groups. The eight different degrees of deacetylation from 12.5% to 100% were taken into account. We found an increasing linear trend (R2 = 0.97) between deacetylation degree and the collagen-chitosan interaction energy. This can be explained by replacing weak hydrophobic contacts with more stable hydrogen bonds involving amino groups in N-deacetylated chitosan moieties. In this study, the properties of chitosan were compared with hyaluronic acid, which is a natural component of synovial fluid and cartilage. As we found, when the degree of deacetylation of chitosan was greater than 0.4, it exhibited a higher affinity for collagen than in the case of hyaluronic acid.

Matter-Aggregating Low-Dimensional Nanostructures at the Edge of the Classical vs. Quantum Realm.

This commentary tackles the subtle at-the-edge problem of passing locally by a mesoscopic matter-aggregating system from a classical stochastic to a quantum stochastic description. A d-dimensional entropy-productive aggregation of the matter is taken as the starting point. Then, a dimensional reduction towards a one-dimensional quantum-wire type matter-aggregation system is proposed, resulting in postponing surface-tension conditions for the effectively d = 1-dimensional quantum-wire type or nanorod-like cluster/polycrystal, which is qualitatively consistent with a physical-metallurgical (high-temperature) Louat's grain growth model. A certain recuperative interplay based on maneuvering between subtle temperature rises applied to the system under study while maintaining its quantum character (the so-called Nelson's quantum-stochastic procedure) within the limits of a vanishing Planck's constant, involved in the diffusivity measure of the aggregation, is discussed. Certain applications towards the formation of d = 1-dimensional semiconductors and other nanostructures (possibly using soft materials or (bio)polymeric materials such as nanofibers) are envisioned. As a special example, one may propose a nanotechnological process which is termed the Van der Waals heteroepitaxy. The process itself contains the main quantum vs. classical crossover due to the involvement of weak repulsion (quantum) vs. attraction (treated classically) interactions, which are represented by a Lennard-Jones-type potential.

Changes of Conformation in Albumin with Temperature by Molecular Dynamics Simulations.

This work presents the analysis of the conformation of albumin in the temperature range of 300 K - 312 K , i.e., in the physiological range. Using molecular dynamics simulations, we calculate values of the backbone and dihedral angles for this molecule. We analyze the global dynamic properties of albumin treated as a chain. In this range of temperature, we study parameters of the molecule and the conformational entropy derived from two angles that reflect global dynamics in the conformational space. A thorough rationalization, based on the scaling theory, for the subdiffusion Flory-De Gennes type exponent of 0 . 4 unfolds in conjunction with picking up the most appreciable fluctuations of the corresponding statistical-test parameter. These fluctuations coincide adequately with entropy fluctuations, namely the oscillations out of thermodynamic equilibrium. Using Fisher's test, we investigate the conformational entropy over time and suggest its oscillatory properties in the corresponding time domain. Using the Kruscal-Wallis test, we also analyze differences between the root mean square displacement of a molecule at various temperatures. Here we show that its values in the range of 306 K - 309 K are different than in another temperature. Using the Kullback-Leibler theory, we investigate differences between the distribution of the root mean square displacement for each temperature and time window.

Information and Statistical Measures in Classical vs. Quantum Condensed-Matter and Related Systems.

The presented editorial summarizes in brief the efforts of ten (10) papers collected by the Special Issue (SI) "Condensed-Matter-Principia Based Information & Statistical Measures: From Classical to Quantum". The SI called for papers dealing with condensed-matter systems, or their interdisciplinary analogs, for which well-defined classical statistical vs. quantum information measures can be inferred while based on the entropy concept. The SI has mainly been rested upon objectives addressed by an international colloquium held in October 2019, at the University of Science and Technology (UTP) Bydgoszcz, Poland (see http://zmpf.imif.utp.edu.pl/rci-jcs/rci-jcs-4/), with an emphasis placed on the achievements of Professor Gerard Czajkowski (PGC). PGC commenced his research activity with diffusion-reaction (open) systems under the supervision of Roman S. Ingarden (Torun), a father of Polish synergetics, and original thermodynamic approaches to self-organization. The active cooperation of PGC mainly with German physicists (Friedrich Schloegl, Aachen; Werner Ebeling, Berlin) ought to be underlined. Then, the development of Czajkowski's research is worth underscoring, moving from statistical thermodynamics to solid state theory, pursued in terms of nonlinear solid-state optics (Franco Bassani, Pisa), and culminating very recently with large quasiparticles, termed Rydberg excitons, and their coherent interactions with light.

On (sub)mesoscopic scale peculiarities of diffusion driven growth in an active matter confined space, and related (bio)material realizations.

Diffusion in a confined space becomes an extremely important problem with many versatile applications, ranging from biomedical to biotechnological, and involving functional and smart (bio)materials. In this study, we have shown that the well-known Mullins-Sekerka approach to morphological stability of the diffusional non-ideal sphere's growth, for which a confinement factor disappears, is a firm starting point for further questions. It has two modifications and/or extensions for which the confinement factor is involved readily and becomes (in)finite firstly for microscale (or micrometer scale) involving biomatter packing phenomena. They are also applicable for nanoscopic biomaterial arrangements for which very tightly packed material and active-matter including outcomes of subdiffusive proveniency would manifest, as it has already been observed for the protein crystal growth in pores and globule-to-coil crossover phenomena.

Correction: Physical crosslinking of hyaluronic acid in the presence of phospholipids in an aqueous nano-environment.

Correction for 'Physical crosslinking of hyaluronic acid in the presence of phospholipids in an aqueous nano-environment' by Piotr Beldowski et al., Soft Matter, 2018, DOI: 10.1039/c8sm01388h.

Physical crosslinking of hyaluronic acid in the presence of phospholipids in an aqueous nano-environment.

Hyaluronic acid and phospholipids are two components in the synovial joint cavity that contribute to joint lubrication synergistically. Molecular dynamics simulations were performed and hydrogen bonds in hyaluronic acid were analyzed to identify specific sites that are responsible for its physical cross-linking. Two molecular masses of hyaluronic acid, 10 kDa and 160 kDa, were considered. We use molecular dynamics simulations and the small world network approach to investigate dynamic couplings using a distance map applied to oxygen atoms in a chain of hyaluronic acid in the presence of phospholipids and water. The distance characterizing the coupling can be defined in various ways to bring out the most evident differences between various scenarios of the polymer chain conformation We show herein a physical distance understood as H-bond length and classes of these distances which are defined in a coarse-grained picture of the molecule. Simulation results indicate that addition of phospholipids has little influence on hyaluronic acid crosslinking. However, longer chains and addition of lipids promote appreciably long lasting (resilient) networks that may be of importance in biological systems. Specific sites for hydrogen bonding of phospholipids to hyaluronic acid have also been identified.

The Anomalies of Hyaluronan Structures in Presence of Surface Active Phospholipids-Molecular Mass Dependence.

Interactions between hyaluronan (A-) and phospholipids play a key role in many systems in the human body. One example is the articular cartilage system, where the synergistic effect of such interactions supports nanoscale lubrication. A molecular dynamics simulation has been performed to understand the process of formation of hydrogen bonds inside the hyaluronan network, both in the presence and absence of phospholipids. Additionally, the effect of the molecular mass of (A-) was analyzed. The main finding of this work is a robust demonstration of the optimal parameters (H-bond energy, molecular mass) influencing the facilitated lubrication mechanism of the articular cartilage system. Simulation results show that the presence of phospholipids has the greatest influence on hyaluronan at low molecular mass. We also show the specific sites of H-bonding between chains. Simulation results can help to understand how hyaluronan and phospholipids interact at several levels of articular cartilage system functioning.

Entropy Production Associated with Aggregation into Granules in a Subdiffusive Environment.

We study the entropy production that is associated with the growing or shrinking of a small granule in, for instance, a colloidal suspension or in an aggregating polymer chain. A granule will fluctuate in size when the energy of binding is comparable to k B T , which is the "quantum" of Brownian energy. Especially for polymers, the conformational energy landscape is often rough and has been commonly modeled as being self-similar in its structure. The subdiffusion that emerges in such a high-dimensional, fractal environment leads to a Fokker-Planck Equation with a fractional time derivative. We set up such a so-called fractional Fokker-Planck Equation for the aggregation into granules. From that Fokker-Planck Equation, we derive an expression for the entropy production of a growing granule.

Anomalous Behavior of Hyaluronan Crosslinking Due to the Presence of Excess Phospholipids in the Articular Cartilage System of Osteoarthritis.

Lubrication of articular cartilage is a complex multiscale phenomenon in synovial joint organ systems. In these systems, synovial fluid properties result from synergistic interactions between a variety of molecular constituent. Two molecular classes in particular are of importance in understanding lubrication mechanisms: hyaluronic acid and phospholipids. The purpose of this study is to evaluate interactions between hyaluronic acid and phospholipids at various functionality levels during normal and pathological synovial fluid conditions. Molecular dynamic simulations of hyaluronic acid and phospholipids complexes were performed with the concentration of hyaluronic acid set at a constant value for two organizational forms, extended (normal) and coiled (pathologic). The results demonstrated that phospholipids affect the crosslinking mechanisms of hyaluronic acid significantly and the influence is higher during pathological conditions. During normal conditions, hyaluronic acid and phospholipid interactions seem to have no competing mechanism to that of the interaction between hyaluronic acid to hyaluronic acid. On the other hand, the structures formed under pathologic conditions were highly affected by phospholipid concentration.

Molecular Dynamic Analysis of Hyaluronic Acid and Phospholipid Interaction in Tribological Surgical Adjuvant Design for Osteoarthritis.

Tribological surgical adjuvants constitute a therapeutic discipline made possible by surgical advances in the treatment of damaged articular cartilage beyond palliative care. The purpose of this study is to analyze interactions between hyaluronic acid and phospholipid molecules, and the formation of geometric forms, that play a role in the facilitated lubrication of synovial joint organ systems. The analysis includes an evaluation of the pathologic state to detail conditions that may be encountered by adjuvants during surgical convalescence. The synovial fluid changes in pH, hyaluronic acid polydispersity, and phospholipid concentration associated with osteoarthritis are presented as features that influence the lubricating properties of adjuvant candidates. Molecular dynamic simulation studies are presented, and the Rouse model is deployed, to rationalize low molecular weight hyaluronic acid behavior in an osteoarthritic environment of increased pH and phospholipid concentration. The results indicate that the hyaluronic acid radius of gyration time evolution is both pH- and phospholipid concentration-dependent. Specifically, dipalmitoylphosphatidylcholine induces hydrophobic interactions in the system, causing low molecular weight hyaluronic acid to shrink and at high concentration be absorbed into phospholipid vesicles. Low molecular weight hyaluronic acid appears to be insufficient for use as a tribological surgical adjuvant because an increased pH and phospholipid concentration induces decreased crosslinking that prevents the formation of supramolecular lubricating forms. Dipalmitoylphosphatidylcholine remains an adjuvant candidate for certain clinical situations. The need to reconcile osteoarthritic phenotypes is a prerequisite that should serve as a framework for future adjuvant design and subsequent tribological testing.

Hyaluronic acid and phospholipid interactions useful for repaired articular cartilage surfaces-a mini review toward tribological surgical adjuvants.

This mini review is focused on the emerging nexus between the medical device and pharmaceutical industries toward the treatment of damaged articular cartilage. The physical rationale of hyaluronic acid and phospholipid preparations as tribological surgical adjuvants for repaired articular cartilage surfaces is explored, with directions for possible new research which have arisen due to the therapeutic advance of the physiochemical scalpel. Because synovial joint lubrication regimes become dysfunctional at articular cartilage lesion sites as a result of the regional absence of the surface active phospholipid layer and its inability to reform without surgical repair, hyaluronic acid and phospholipid intra-articular injections have yielded inconsistent efficacy outcomes and only short-term therapeutic benefits mostly due to non-tribological effects. Parameters for hydrophobic-polar type interactions as applied to the lubricating properties of normal and osteoarthritic synovial fluid useful for repaired articular cartilage surfaces are discussed.

Dynamical Systems Theory in Quantitative Psychology and Cognitive Science: A Fair Discrimination between Deterministic and Statistical Counterparts is Required.

This article addresses a set of observations framed in both deterministic as well as statistical formal guidelines. It operates within the framework of nonlinear dynamical systems theory (NDS). It is argued that statistical approaches can manifest themselves ambiguously, creating practical discrepancies in psychological and cognitive data analyses both quantitatively and qualitatively. This is sometimes termed in literature as 'questionable research practices.' This communication points to the demand for a deeper awareness of the data 'initial conditions, allowing to focus on pertinent evolution constraints in such systems.' It also considers whether the exponential (Malthus-type) or the algebraic (Pareto-type) statistical distribution ought to be effectively considered in practical interpretations. The role of repetitive specific behaviors by patients seeking treatment is examined within the NDS frame. The significance of these behaviors, involving a certain memory effect seems crucial in determining a patient's progression or regression. With this perspective, it is discussed how a sensitively applied hazardous or triggering factor can be helpful for well-controlled psychological strategic treatments; those attributable to obsessive-compulsive disorders or self-injurious behaviors are recalled in particular. There are both inherent criticality- and complexity-exploiting (reduced-variance based) relations between a therapist and a patient that can be intrinsically included in NDS theory.

The amphoteric effect on friction between the bovine cartilage/cartilage surfaces under slightly sheared hydration lubrication mode.

The amphoteric effect on the friction between the bovine cartilage/cartilage contacts has been found to be highly sensitive to the pH of an aqueous solution. The cartilage surface was characterized using a combination of the pH, wettability, as well as the interfacial energy and friction coefficient testing methods to support lamellar-repulsive mechanism of hydration lubrication. It has been confirmed experimentally that phospholipidic multi-bilayers are essentially described as lamellar frictionless lubricants protecting the surface of the joints against wear. At the hydrophilicity limit, the low friction would then be due to (a) lamellar slippage of bilayers and (b) a short-range (nanometer-scale) repulsion between the interfaces of negatively charged (PO4(-)) cartilage surfaces, and in addition, contribution of the extracellular matrix (ECM) collagen fibers, hyaluronate, proteoglycans aggregates (PGs), glycoprotein termed lubricin and finally, lamellar PLs phases. In this paper we demonstrate experimentally that the pH sensitivity of cartilage to friction provides a novel concept in joint lubrication on charged surfaces.

Some conceptual thoughts toward nanoscale oriented friction in a model of articular cartilage.

This work presents a conceptual framework as to how a deficit in the synovial-fluid content, exemplified by hyaluronan or any other amphiphilic species, is capable of decisively altering the complex lubrication and wear conditions observed clinically in articular cartilage. The effect is revealed in (non)stationary regimes if the cartilage is subjected to some normal periodic load, revealing over its exploitation time increasingly dissipative, in general entropy-addressing, characteristics. It can be hypothesized that a Grotthuss-type proton transport physiology-concerning mechanism in channel-like, phospholipid-water cartilage's articulating nanospaces will be responsible for the expression of the lubrication mode. The corresponding wear involving overall change is then manifested adequately in the stationary regime, and in a viable system-parametric correlation with its lubrication counterpart. Certain analytic formulae for the nanoscale oriented coefficient of friction, involving generically H-bonds breaking mechanism, and pointing to some local-viscosity context, have been proposed for fitting the experimental data and clinical observations involving proton management at articular cartilage surfaces.

The role of lamellate phospholipid bilayers in lubrication of joints.

This study aims to determine the effect of progressive loss of the surface active phospholipids on the characteristics, and hence tribological function of articular cartilage. In accordance to Hill's hypothesis, 3-7 lipid bilayers at pH 7.4 operate as the solid lubricant in the cartilage-cartilage interface during physiological function. These bilayers are known to be depleted during cartilage degeneration. This study models this loss of phospholipid bilayers, studying experimentally both wet and dry cartilage surfaces, measuring surface wettability, and friction coefficient under a constant stress of 1.2 MPa. The results demonstrate that the friction coefficient increases gradually with loss of the phospholipid bilayers, and gains in value with decrease in wettability.