关节软骨:关节软骨可以被认为是一种智能材料吗?

Zenon P, Michał S, Bozena K
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The understanding of AC amphoteric surface will be essential for understanding the joints lubrication mechanism, the effective repair and regeneration of the degraded knee joint. The isoelectric point, IEP, is at a pH of ~ 4 when a PL molecule carries no net electrical charge H2N (CH2)n PO4H-R1R2  H3N + (CH2)n PO4 -R1R2. Changes of the interfacial energy correspond to the amino (-NH3 +→ -NH2) transition with a low pH, after IEP the phosphate (-PO4H → -PO4 -) transition at a higher pH range of 4 to 6.5. The isoelectric point, IEP, with the pH at which a phospholipid molecule carries no net electrical charge. The wetted surfaces (pH~6.5 to 9.5) of the phospholipid membranes are negatively charged (–PO4 -). Biosurface wettability can be measured relative to the differences in the charge density of the functional phosphate (–PO4 -) group. In this regard, the wettability of a hydrated surface is characterized by the concentration of charged anionic phosphate (–PO4 -) groups that are deactivated when the surface is dehydrated. The dehydration of the phospholipid bilayer surface activates hydrophobic groups, R (CH2)n due to the formation World J Gastroenterol Hepatol Endosc Volume: 3.3 1/2 of a hydrophobic monolayer, Figure 1. The hydrophilic surface in the course of dehydration, for example, via air-drying, undergoes a slow increase in the wettability contact angle indicating conformational changes in the surface (flip-flop) phospholipid molecules. Poor lubrication in animal joints, particularly on the articular surface of cartilage, can be attributed to deterioration of the bilayer surface, where the wettability or contact angle (θ) changes from 104° to less than 70° (Wettability was measured in air-dry condition) (Figure 2). Figure 1 (a, b): The smart-surface constitution of superficial phospholipid bilayer of articular cartilage in (a) wet (hydrophilic) and (b) at air-dry condition (hydrophobic). Figuer 1(c): The profiles of the interfacial surface energy (γ ) of spherical lipid bilayer model “bell-shaped curve” vs. pH of buffer solution. (a) ( pH 0.2 to 4.0 (-NH3 +→ -NH2.). (b) (pH 4.0 to 6.5 ) (-PO4H → -PO4 -) IEP : H2N (CH2)n PO4H-R1R2  H3N (CH2)n PO4 -R1R2 Figure 2: (A) The hydrophilic model of cartilage surface (B) shows the cartilage transformation of the hydrophilic bilayer at wet condition to hydrophobic monolayer (at air-dry room condition). The lamellar-repulsive mechanism is supported by phospholipid lamellar phases and charged macromolecules from synovial fluid between negatively charged cartilage surfaces. The low friction results as a consequence of a short-range hydration repulsion (nanometer-scale) between the interface of negatively charged (-PO4 -) cartilage surfaces and contribution of macromolecules in the synovial fluid and most importantly a lamellar slippage of bilayers. The acid-base properties of the phospholipid bilayer significantly influence their wettability and surface friction properties Figure 2. 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引用次数: 0

摘要

研究表明,软骨的“智能表面”在潮湿时是高度亲水的,在风干时是疏水的。发现双分子层的最小表面能在很宽的pH范围内(6.5至9.5)分布。双分子层数量的减少改变了润湿性,降低了PL润滑油的性能。综上所述,软骨智能材料可以对pH值和湿度的变化做出显著的反应。关节软骨(AC)的生物组织在自然状态下是两性的,在风干条件下表面由亲水性变为疏水性(图1a, b)。球形脂质双层模型的界面表面能(γ)与pH值的“钟形曲线”变化使表面电荷从正、中性变为负,关节软骨可以被命名为“智能材料”(图1c)。了解AC两性表面对了解关节润滑机制、退化膝关节的有效修复和再生具有重要意义。当PL分子不带净电荷时,等电点IEP为~ 4,H2N (CH2)n PO4H-R1R2H3N + (CH2)n PO4 -R1R2。界面能的变化对应于低pH下的氨基(- nh3 +→- nh2)转变,IEP后的磷酸(- po4h→- po4 -)转变在更高的pH范围(4 ~ 6.5)。等电点,IEP,在该等电点上磷脂分子不带净电荷。磷脂膜的湿润表面(pH~6.5 ~ 9.5)带负电荷(- po4 -)。生物表面润湿性可以通过功能磷酸(- po4 -)基团的电荷密度差异来测量。在这方面,水合表面的润湿性是由带电的阴离子磷酸盐(- po4 -)基团的浓度表征的,这些基团在表面脱水时失活。磷脂双分子层表面的脱水激活疏水基团R (CH2)n,形成World J Gastroenterol Hepatol Endosc体积:疏水单层的3.3 /2,图1。亲水表面在脱水过程中,例如通过空气干燥,润湿性接触角缓慢增加,这表明表面磷脂分子的构象发生了变化(翻转)。动物关节的润滑不良,特别是软骨关节表面的润滑不良,可归因于双层表面的恶化,其中润湿性或接触角(θ)从104°变化到小于70°(润湿性在风干条件下测量)(图2)。图1 (a, b): (a)潮湿(亲水)和(b)风干条件下(疏水)关节软骨表面磷脂双层的智能表面构成。图1(c):球形脂质双层模型界面表面能(γ)随缓冲溶液pH的“钟形曲线”分布图。(a) (pH 0.2 ~ 4.0 (-NH3 +→-NH2)。(b) (pH 4.0 ~ 6.5) (- po4h→-PO4 -) IEP: H2N (CH2)n PO4H-R1R2H3N (CH2)n PO4 - r1r2图2:(A)软骨表面的亲水性模型(b)显示了软骨在潮湿条件下亲水性双层向疏水性单层(在风干室内条件下)的转变。片层排斥机制是由磷脂片层相和带负电荷的软骨表面之间的滑膜液中的带电大分子支持的。低摩擦是由于带负电荷的(- po4 -)软骨表面界面之间的短距离水合排斥(纳米级)和滑液中大分子的贡献,以及最重要的双层板层滑动的结果。磷脂双分子层的酸碱性质显著影响其润湿性和表面摩擦性能(图2)。综上所述,软骨智能材料可以对pH值和湿度的变化做出显著的反应。
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Articular Cartilage: Can Articular Cartilage be Considered a Smart Material?
It has been shown that the “smart surface” of cartilage is highly hydrophilic when wet and hydrophobic when air-dry. The minimum surface energy of the bilayer was found to spread over a wide range of pH (6.5 to 9.5). The decreased number of bilayers changed the wettability and lowered the PL lubricant properties. In conclusion, a cartilage smart material can significantly react to changes pH and moisture. The biological tissue of the articular cartilage (AC) is amphoteric in its natural condition transforming surface from the hydrophilic to hydrophobic in air-dry condition (Figure 1 a, b). The profiles of the interfacial surface energy (γ ) of spherical lipid bilayer model „bell-shaped curve” vs. pH change the surface charge from positive, neutral to negative, the articular cartilage can be named a “smart material” (Figure 1c). The understanding of AC amphoteric surface will be essential for understanding the joints lubrication mechanism, the effective repair and regeneration of the degraded knee joint. The isoelectric point, IEP, is at a pH of ~ 4 when a PL molecule carries no net electrical charge H2N (CH2)n PO4H-R1R2  H3N + (CH2)n PO4 -R1R2. Changes of the interfacial energy correspond to the amino (-NH3 +→ -NH2) transition with a low pH, after IEP the phosphate (-PO4H → -PO4 -) transition at a higher pH range of 4 to 6.5. The isoelectric point, IEP, with the pH at which a phospholipid molecule carries no net electrical charge. The wetted surfaces (pH~6.5 to 9.5) of the phospholipid membranes are negatively charged (–PO4 -). Biosurface wettability can be measured relative to the differences in the charge density of the functional phosphate (–PO4 -) group. In this regard, the wettability of a hydrated surface is characterized by the concentration of charged anionic phosphate (–PO4 -) groups that are deactivated when the surface is dehydrated. The dehydration of the phospholipid bilayer surface activates hydrophobic groups, R (CH2)n due to the formation World J Gastroenterol Hepatol Endosc Volume: 3.3 1/2 of a hydrophobic monolayer, Figure 1. The hydrophilic surface in the course of dehydration, for example, via air-drying, undergoes a slow increase in the wettability contact angle indicating conformational changes in the surface (flip-flop) phospholipid molecules. Poor lubrication in animal joints, particularly on the articular surface of cartilage, can be attributed to deterioration of the bilayer surface, where the wettability or contact angle (θ) changes from 104° to less than 70° (Wettability was measured in air-dry condition) (Figure 2). Figure 1 (a, b): The smart-surface constitution of superficial phospholipid bilayer of articular cartilage in (a) wet (hydrophilic) and (b) at air-dry condition (hydrophobic). Figuer 1(c): The profiles of the interfacial surface energy (γ ) of spherical lipid bilayer model “bell-shaped curve” vs. pH of buffer solution. (a) ( pH 0.2 to 4.0 (-NH3 +→ -NH2.). (b) (pH 4.0 to 6.5 ) (-PO4H → -PO4 -) IEP : H2N (CH2)n PO4H-R1R2  H3N (CH2)n PO4 -R1R2 Figure 2: (A) The hydrophilic model of cartilage surface (B) shows the cartilage transformation of the hydrophilic bilayer at wet condition to hydrophobic monolayer (at air-dry room condition). The lamellar-repulsive mechanism is supported by phospholipid lamellar phases and charged macromolecules from synovial fluid between negatively charged cartilage surfaces. The low friction results as a consequence of a short-range hydration repulsion (nanometer-scale) between the interface of negatively charged (-PO4 -) cartilage surfaces and contribution of macromolecules in the synovial fluid and most importantly a lamellar slippage of bilayers. The acid-base properties of the phospholipid bilayer significantly influence their wettability and surface friction properties Figure 2. In conclusion, a cartilage smart material can significantly react to changes pH and moisture.
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