Natural joints: Boundary lubrication and antiphospholipid syndrome (APS).

The paper shows that osteoporosis (OA) changes the SF content and the lipid profile substantially. To estimate the implication of the lipid environment in case the articular cartilage (AC) changes, we measured friction coefficient normal samples, with early and late stages of (OA). During joint inflammation and osteoarthritis, enzymatically activated ß2-Glycoprotein I is transformed into antibody conformation. Our hypothesis about cartilage degradation of PL bilayers by antibodies (ß2-Glycoprotein I) is considering antiphospholipid syndrome (APS), which was not discussed in the literature before. Deactivated PL molecule has no ability to form bilayers, lamellar phases, and liposomes. The phospholipid content in synovial fluid (SF) during joint inflammation, osteoarthritis, and rheumatoid arthritis is significantly higher (2-3 times) above the normal concentration of PL, and has a poor boundary-lubricating ability is deactivated.

Articular cartilage. Strong adsorption and cohesion of phospholipids with the quaternary ammonium cations providing satisfactory lubrication of natural joints.

Much evidence supports the hypothesis that surface-active phospholipid (SAPL) molecules on articular cartilage (AC) adsorbed to negatively-charged proteoglycan matrix form phospholipid (membrane), are negatively charged surface (-PO4-) and hydrophilic. In Hills cartilage model (1984) phospholipids adsorbed to cartilage surface act as boundary lubricants making the surface extremely hydrophobic. Hydrophobic surface of AC has gained no support in all experimental facts presented in this paper and the current literature showing that AC is amphoteric and hydrophilic with the negatively charged surface (-PO4-). The interfacial energy of the model membrane of spherical lipid bilayers evident from phosphatidylcholine "bell-shaped curve" has amphoteric character and lowest energy in lubrication at a pH 7.4 ± 1 of the natural joint.

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.

Repulsive surfaces and lamellar lubrication of synovial joints.

Surface-active phospholipid (SAPL) secreted in the synovial joint plays an important role in cartilage integrity. In healthy joints, phospholipid multibilayers coat the cartilage surface, providing boundary lamellar-repulsive hydration lubrication. Current mechanism for lubrication of synovial joints, as well as the physical and chemical nature of the cartilage surface is discussed. Friction between phospholipid (PL) bilayers attached to cartilage surfaces is considered including a discussion on the recent observation of an extreme friction reduction as a consequence of a less charged hydrophilic cartilage surface. It is proposed that the highly efficient lubrication occurring in natural joints arises from the presence of negatively charged cartilage surfaces. The lamellar-repulsive mechanisms for the reduction of friction is supported by phospholipid lamellar phases and charged macromolecules residing between contacting cartilage surfaces at pH ∼7.4.

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.

Tribological efficacy and stability of phospholipid-based membrane lubricants in varying pH chemical conditions.

In this study, the authors examine the influence of joint chemical environment by measuring changes in the tribological properties (friction coefficient and charge density) of contacting surfaces of normal and degenerated cartilage samples in bath solutions of varying pH (2.0-9.0). Bovine articular cartilage samples (n = 54) were subjected to several surface measurements, including interfacial energy, contact angle, and friction coefficient, at varying pH. The samples were delipidized and then subjected to the same measurement protocols. Our results reveal that the interfacial energy and charge density, which have been shown to be related to friction coefficient, decrease with pH in the acidic range and approach constant values at physiological (or synovial fluid) pH of 7.4 and beyond it, i.e., toward basic pH domain. The authors conclude that this rather complex response explains the long-term efficacy with respect to ageing and associated pH changes, of the phospholipid layers that facilitate the almost frictionless, hydration-lubrication involving contact in the mammalian musculoskeletal system.

The Probable Explanation for the Low Friction of Natural Joints.

The surface of an articular cartilage, coated with phospholipid (PL) bilayers, plays an important role in its lubrication and movement. Intact (normal) and depleted surfaces of the joint were modelled and the pH influence on the surface interfacial energy, wettability and friction were investigated. In the experiments, the deterioration of the PL bilayer was controlled by its wettability and the applied friction. The surrounding fluid of an undamaged articular cartilage, the synovial fluid, has a pH value of approximately 7.4. Buffer solutions were formulated to represent the synovial fluid with various pH values. It was found that the surface interfacial energy was stabilised at its lowest values when the pH varied between 6.5 and 9.5. These results suggested that as the PL bilayers deteriorated, the hydration repulsion mechanism became less effective as friction increased. The decreased number of bilayers changed the wettability and lowered PL lubricant properties.

Lamellar slippage of bilayers--a hypothesis on low friction of natural joints.

The cartilage's amphoteric surface behavior is a physical phenomenon in biological lubrication. However, there is a lack of knowledge on amphoteric phospholipids bilayers and in overcoming friction in cartilage joints. In this paper, friction experiments were conducted, and the cartilage's surface was characterized using pH and wettability, while the interfacial energy and coefficients were determined. The lamellar slippage of bilayers and a short-range repulsion between the interfaces of negatively charged (-PO4 (-)) cartilage surfaces resulted in low frictional properties of the joint.

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.

Relationship between wettability and lubrication characteristics of the surfaces of contacting phospholipid-based membranes.

The wettability of the articular surface of cartilage depends on the condition of its surface active phospholipid overlay, which is structured as multi-bilayer. Based on a hypothesis that the surface of cartilage facilitates the almost frictionless lubrication of the joint, we examined the characteristics of this membrane surface entity in both its normal and degenerated conditions using a combination of atomic force microscopy, contact angle measurement, and friction test methods. The observations have led to the conclusions that (1) the acid-base equilibrium condition influences the lubrication effectiveness of the surface of cartilage and (2) the friction coefficient is significantly dependent on the hydrophobicity of the surface of the tissue, thereby confirming the hypothesis tested in this paper. Both wettability angle and interfacial energy were obtained for varying conditions of the cartilage surface both in its wet, dry and lipid-depleted conditions. The interfacial energy also increased with mole fraction of the lipid species reaching an asymptotic value after 0.6. Also, the friction coefficient was found to decrease to an asymptotic level as the wettability angle increased. The result reveal that the interfacial energy increased with pH till pH = 4.0, and then decreased from pH = 4.0 to reach equilibrium at pH = 7.0.

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.

A microanalytical study of the surfaces of normal, delipidized, and artificially "resurfaced" articular cartilage.

The surface amorphous layer of articular cartilage is of primary importance to its load-bearing and lubrication function. This lipid-filled layer is degraded/disrupted or eliminated when cartilage degenerates due to diseases. This article examines further the characteristic of this surface overlay using a combination of microscopy and imaging methods to evaluate the hypothesis that the surface of articular cartilage can be repaired by exposing degraded cartilage to aqueous synthetic lipid mixtures. The preliminary results demonstrate that it is possible to create a new surface layer of phospholipids on the surface of cartilage following artificial lipid removal, but such a layer does not possess enough mechanical strength for physiological function when created with either unsaturated palmitoyl-oleoyl-phosphatidylcholine or saturated dipalmitoyl-phosphatidylcholine component of joint lipid composition alone. We conclude that this may be due to low structural cohesivity, inadequate time of exposure, and the mix/content of lipid in the incubation environment.

Conceptualisation of articular cartilage as a giant reverse micelle: a hypothetical mechanism for joint biocushioning and lubrication.

Phospholipid (PL) molecules form the main structure of the membrane that prevents the direct contact of opposing articular cartilage layers. In this paper we conceptualise articular cartilage as a giant reverse micelle (GRM) in which the highly hydrated three-dimensional network of phospholipids is electrically charged and able to resist compressive forces during joint movement, and hence loading. Using this hypothetical base, we describe a hydrophilic-hydrophilic (HL-HL) biopair model of joint lubrication by contacting cartilages, whose mechanism is reliant on lamellar cushioning. To demonstrate the viability of our concept, the electrokinetic properties of the membranous layer on the articular surface were determined by measuring via microelectrophoresis, the adsorption of ions H, OH, Na and Cl on phospholipid membrane of liposomes, leading to the calculation of the effective surface charge density. The surface charge density was found to be -0.08+/-0.002cm(-2) (mean+/-S.D.) for phospholipid membranes, in 0.155M NaCl solution and physiological pH. This value was approximately five times less than that measured in 0.01M NaCl. The addition of synovial fluid (SF) to the 0.155M NaCl solution reduced the surface charge density by 30% which was attributed to the binding of synovial fluid macromolecules to the phospholipid membrane. Our experiments show that particles charge and interact strongly with the polar core of RM. We demonstrate that particles can have strong electrostatic interactions when ions and macromolecules are solubilized by reverse micelle (RM). Since ions are solubilized by reverse micelle, the surface entropy influences the change in the charge density of the phospholipid membrane on cartilage surfaces. Reverse micelles stabilize ions maintaining equilibrium, their surface charges contribute to the stability of particles, while providing additional screening for electrostatic processes.

Comparison of inductively coupled plasma-mass spectrometry and radiochemical techniques for total uranium in environmental water samples.

Inductively coupled plasma-mass spectrometry (ICP-MS) method EPA 200.8 is gradually finding acceptance as an alternative to uranium analysis. A comparison of the ICP-MS with the accepted radiochemical method EPA 908.0 has been carried out based on data from laboratory control standards, national proficiency test samples, and environmental and drinking water samples from the State of Utah. The method detection limit (MDL) for ICP-MS was determined to be 0.017 microg/L or (0.011 pCi/L), and the minimum reporting limit (MRL) was 0.17 microg/L (MDL x 10) or (0.11 pCi/L). The minimum reporting limit for radiochemical 908.0 method is 1 pCi/L. Our spiked matrix recoveries, spiked blank samples, and reference materials deviate only a few percentage from the listed true values. Results demonstrate that the ICP-MS is a superior analytical tool for the determination of uranium in drinking and environmental waters at concentrations required by the United States Environmental Protection Agency.