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Publication numberCN102727933 B
Publication typeGrant
Application numberCN 201210031571
Publication dateJun 5, 2013
Filing dateFeb 13, 2012
Priority dateFeb 13, 2012
Also published asCN102727933A
Publication number201210031571.2, CN 102727933 B, CN 102727933B, CN 201210031571, CN-B-102727933, CN102727933 B, CN102727933B, CN201210031571, CN201210031571.2
Inventors王韶亮, 樊东力, 张一鸣, 王一丞, 石小花, 杨芷
Applicant中国人民解放军第三军医大学第二附属医院
Export CitationBiBTeX, EndNote, RefMan
External Links: SIPO, Espacenet
Novel silicone rubber-hydroxy apatite composite material and preparation method thereof
CN 102727933 B
Abstract  translated from Chinese
本发明公开了一种硅橡胶-羟基磷灰石复合材料,包括硅橡胶层和羟基磷灰石涂层,硅橡胶层和羟基磷灰石涂层通过硫化成型的方式制为一体结构;其制备方法,包括硅橡胶制模和羟基磷灰石粉末喷涂等步骤;采用本发明所属的制备方法所得的硅橡胶-羟基磷灰石复合材料,既有硅橡胶(SR)良好的生物力学性能,又具有表面活性,与周围组织紧密结合,不会发生变形移位;同时还克服了单用硅橡胶(SR)和羟基磷灰石(HA)造成的包膜挛缩、颗粒游走或材料断裂等缺点;通过大量临床试验证明,可以安全可靠的用于美容整形的创伤与修复手术中,效果十分明显。 The present invention discloses a silicone rubber - hydroxyapatite composite materials, including silicone rubber layer and hydroxyapatite coatings, silicone rubber layer and hydroxyapatite coating by way of vulcanization molding system as a whole structure; its preparation methods, including silicone rubber molding and hydroxyapatite powder coating step; with which this invention belongs preparation resulting silicone rubber - hydroxyapatite composite materials, both silicone rubber (SR) good biomechanical properties, and surface active, closely integrated with the surrounding tissue, not deformed shift; also overcome the single-use silicone rubber (SR) and hydroxyapatite (HA) due to capsular contracture, particle migration or fracture and other shortcomings ; through a large number of clinical trials to prove, it is safe and reliable for cosmetic surgery and reconstructive surgery trauma, the effect is very obvious.
Claims(3)  translated from Chinese
1.一种硅橡胶一轻基磷灰石复合材料的制备方法,所述硅橡胶一轻基磷灰石复合材料包括硅橡胶层(Ia)和羟基磷灰石涂层(lb),硅橡胶层(Ia)和羟基磷灰石涂层(Ib)通过硫化成型的方式制为一体结构,其特征在于:所述方法包括以下步骤: a、在温度为20C、湿度为50%的条件下,将双组份医用液态硅橡胶的A、B组分按体积比1:1的比例混合,搅拌均匀后注入金属平板模具中,将其在-0.1MPa的真空条件下静置30min后取出; b、在温度20C的条件下静置硫化、固化5h后,将粒径为40 μ m〜150 μ m的羟基磷灰石颗粒均匀地喷涂于硅橡胶表面,静置30min后固化完全即可。 1. A silicone rubber a light hydroxyapatite composite material, said silicone rubber of a light hydroxyapatite composite comprises a silicone rubber layer (Ia) and a hydroxyapatite coating (lb), silicone rubber layer (Ia) and hydroxyapatite coating (Ib) by vulcanization molding manner as an integrated structure, characterized in that: said method comprising the steps of: a, at a temperature of 20 C, humidity of 50% for Under the two-component liquid silicone rubber for medical A, B component volume ratio of 1: 1 ratio, stir flat metal injection mold, allowed to stand under vacuum conditions -0.1MPa removed after 30min ; b, at a temperature of 20 C allowed to stand for curing conditions, curing after 5h, the particle size of 40 μ m~150 μ m hydroxyl apatite particles uniformly sprayed on the surface of silicone rubber, is completely solidified upon standing 30min can be.
2.根据权利要求1所述的制备方法,其特征在于,所述硅橡胶的厚度为0.5〜2mm。 2. The production method according to claim 1, characterized in that the thickness of the silicone rubber is 0.5~2mm.
3.根据权利要求1或2所述的制备方法,其特征在于:步骤a中采用的金属平板模具为长方体箱体结构,其长X宽X高的尺寸要求为IOOmmX IOOmmX 2mm、IOOmmX IOOmmX Imm或IOOmmX I OOmmX0.5mm。 3. The preparation of claim 1 or claim 2, wherein: the steps used in a metal mold for flat rectangular box structure, its length X width X height size requirements for IOOmmX IOOmmX 2mm, IOOmmX IOOmmX Imm or IOOmmX I OOmmX0.5mm.
Description  translated from Chinese

一种硅橡胶-羟基磷灰石复合材料及其制备方法 A silicone Rubber - hydroxyapatite composite material and its preparation method

技术领域 FIELD

[0001] 本发明涉及一种复合材料及其制备方法,特别涉及一种具有高表面活性的医用硅橡胶一轻基磷灰石复合材料及其制备方法。 [0001] The present invention relates to a composite material and its preparation method, particularly relates to a high surface activity of medical silicone rubber a light hydroxyapatite composite material and preparation method.

背景技术 BACKGROUND

[0002] 创伤与修复一直是整形外科领域的重要研究课题,目前临床上对先天性或外伤等原因造成的体表组织器官的畸形和缺损主要采用软组织材料植入法进行修复,这种方法符合现代医学的发展趋势:以“无创修复”替代“创伤修复创伤”。 [0002] trauma and repair has been an important research topic in the field of plastic surgery, the current clinical congenital or trauma causes the surface tissue and organ deformities and defects repaired primarily soft tissue implantation materials, in line with this approach the development trend of modern medicine: the "non-invasive fix" instead of "wound healing wounds." 但是,在临床应用中发现,将软组织材料(如硅橡胶等)植入人体后,发现它不能与周围组织粘附、结合,易发生变形移位,不能很好的达到整形修复的目的。 However, in the clinical application discovery, after the soft tissue material (such as silicone rubber, etc.) implant into the body, and found that it can not adhere to the surrounding tissue, binding, prone to deformation and shift, not well reach reconstructive purposes. 造成这种现象的主要原因在于:目前应用的软组织材料,其表面呈强烈的疏水性,导致组织细胞的相容性较差,进而纤维结缔组织在材料周围形成包囊,包囊随时间增厚、挛缩,最终使植入材料变形移位。 The main reason for this phenomenon is that: soft tissue material currently in use, its surface was strongly hydrophobic, resulting in poor tissue compatibility, fibrous connective tissue in the surrounding material and thus the formation of cysts, cysts thickened over time contracture, and finally to the implant material deformation displacement. 对该类材料进行合适的表面改性处理,增强其细胞相容性,对提高软组织材料填充后的临床治疗效果,研究材料表面特性与细胞生物学行为之间的关系都有重要的意义。 The class of materials suitable surface modification to enhance its cellular compatibility, to improve the relationship between the clinical outcomes after soft tissue filling material, the surface characteristics of materials and biological behavior between cells has important significance.

[0003] 人工合成的羟基磷灰石(HA)是钙磷陶瓷类生物材料的一种,与人体内骨与牙釉质内天然的羟基磷灰石(HA)组成成分和结晶体结构类似,HA极少引起异物及炎症反应,无毒、无刺激、无排斥反应、不老化、不致敏、不致癌,具有极佳的生物相容性,植入体内和机体的结合能力强,目前在临床得到了广泛应用。 [0003] synthetic hydroxyapatite (HA) is a calcium phosphate ceramic biomaterials, and the human body within the enamel of natural bone and hydroxyapatite (HA) composed of similar composition and crystal structure, HA pole foreign body and cause less inflammation, non-toxic, no stimulation, no rejection, no aging, no allergenic, non carcinogenic, with excellent biocompatibility, strong body and implanted in the body's ability to bind, currently in clinical got widely used. 羟基磷灰石(HA)可以和骨组织发生化学性结合,但由于羟基磷灰石(HA)的韧性高,强度低,烧结成型的块状材料脆性大,因此临床上主要用于填充窝洞性缺损和作为不负重部位的人工骨,用途十分受限。 Hydroxyapatite (HA) and bone tissue can undergo chemical binding, but due to the high hydroxyapatite (HA) toughness, low intensity, sintering of bulk materials brittle, so the patients are used to fill the cavity defect, and as a non-weight-bearing parts of the artificial bone, use is very limited.

[0004] 结合上述两种材料的优缺点,本发明欲发明一种硅橡胶一羟基磷灰石复合材料,集成两种材料的优点,以克服现有技术中存在的不足,扩大该新型复合材料的应用范围。 [0004] The combination of the advantages and disadvantages of these two materials, the present invention is intended to invent a silicone rubber of a hydroxyapatite composite, integrated advantages of both materials, in order to overcome the shortcomings of the prior art, the expansion of the new composite materials range of applications.

发明内容 SUMMARY

[0005] 有鉴于此,本发明的目的是提供一种硅橡胶一羟基磷灰石复合材料及其制备方法,使所得硅橡胶一轻基磷灰石复合材料既有硅橡胶(SR)良好的生物力学性能,又具有良好的表面活性,与周围组织紧密结合,克服了单用硅橡胶(SR)或羟基磷灰石(HA)造成的包膜挛缩、颗粒游走或材料断裂等缺点。 [0005] In view of this, object of the present invention is to provide a silicone rubber, a hydroxyapatite composite material and its preparation method, the resulting silicone rubber a light hydroxyapatite composites both silicone rubber (SR) Good biomechanical properties, but also has good surface activity, closely integrated with the surrounding tissue, to overcome the single-use silicone rubber (SR) or hydroxyapatite (HA) due to capsular contracture, particle migration or fracture and other shortcomings.

[0006] 本发明的目的是通过以下技术方案实现的:一种硅橡胶一羟基磷灰石复合材料,包括硅橡胶层和羟基磷灰石涂层,硅橡胶层和羟基磷灰石涂层通过硫化成型的方式制为一体结构。 [0006] The present invention is achieved by the following technical solutions: a silicone rubber, a hydroxyapatite composite materials, including silicone rubber layer and hydroxyapatite coatings, silicone rubber layer and hydroxyapatite coating by vulcanization molding manner as a unitary structure.

[0007] 其中,娃橡胶层(1a)的厚度为.0.5〜2mm ; [0007] wherein the thickness of the baby rubber layer (1a) is .0.5~2mm;

[0008] 其中,所述轻基磷灰石涂层(lb)的厚度为40〜150 μ m。 [0008] wherein the light hydroxyapatite coating (lb) of thickness 40~150 μ m.

[0009] 另外,本发明的技术方案还包括一种硅橡胶一羟基磷灰石复合材料的制备方法,包括以下步骤: [0009] Further, aspect of the present invention further comprises a silicone rubber of a hydroxyapatite composite material, comprising the steps of:

[0010] a、在温度为20C、湿度为50%的条件下,将双组份医用液态硅橡胶的A、B组分按体积比1:1的比例混合,搅拌均匀后注入金属平板模具中,将其在-0.1MPa的真空条件下静置30min后取出;[0011 ] b、在温度20C的条件下静置硫化、固化5h后,将粒径为40 μ m〜150 μ m的羟基磷灰石颗粒均匀地喷涂于硅橡胶表面,静置30min后固化完全即可。 [0010] a, at a temperature of 20 C, humidity of 50% for the two-component liquid silicone rubber medical A, B component ratio by volume 1: 1 ratio, after injection stir flat metal plate mold, which was allowed to stand under vacuum conditions for 30min -0.1MPa removed; [0011] b, at a temperature of 20 C allowed to stand for curing conditions, curing after 5h, the particle size of 40 μ m~150 μ hydroxyapatite particles m uniformly sprayed on the surface of the silicone rubber, can be completely cured upon standing 30min. [0012] 其中,步骤a中采用的金属平板模具为长方体箱体结构,其尺寸要求为10OmmX IOOmmX 2mm、10OmmX 10OmmX 1mm 或IOOmmX IOOmmX 0.5mm。 [0012] wherein, in step a flat metal plate mold used in a rectangular parallelepiped box structure, the size requirements for 10OmmX IOOmmX 2mm, 10OmmX 10OmmX 1mm or IOOmmX IOOmmX 0.5mm. [0013] 本发明的有益效果:采用本发明所属的制备方法所得的硅橡胶一羟基磷灰石复合材料,既有硅橡胶(SR)良好的生物力学性能,又具有表面活性,与周围组织紧密结合,不会发生变形移位;同时还克服了单用硅橡胶(SR)和羟基磷灰石(HA)造成的包膜挛缩、颗粒游走或材料断裂等缺点;通过大量临床试验证明,可以安全可靠的用于美容整形的创伤与修复手术中,效果十分明显。 [0013] The beneficial effects of the present invention are: apatite composite materials, both silicone rubber (SR) good biomechanical properties of a hydroxyl group was prepared in the silicone rubber obtained by the method of the present invention pertains, and having surface activity, with the surrounding tissue in close combined, will not deform shift; also overcome the single-use silicone rubber (SR) and hydroxyapatite (HA) due to capsular contracture, particle migration or fracture and other shortcomings; proven by numerous clinical trials, can safe for cosmetic surgery and reconstructive surgery trauma, the effect is very obvious. 附图说明[0014] 下面结合附图和实施例对本发明作进一步描述:[0015] 图1为本发明所述的硅橡胶一轻基磷灰石复合材料的结构示意图;[0016] 图2为纯SR用扫描电镜(SEM)观察材料的微观形貌图;[0017] 图3为实施例1所得的HA-SR用扫描电镜(SEM)观察涂层材料的微观形貌图;[0018] 图4为实施例2所得的HA-SR用扫描电镜(SEM)观察涂层材料的微观形貌图;[0019] 图5为对纯SR表面的成分进行分析的X射线光电子能谱图(XPS);[0020] 图6为对实施例1所得的HA-SR材料表面的成分进行分析的X射线光电子能谱图(XPS);[0021] 图7为对实施例2所得的HA-SR材料表面的成分进行分析的X射线光电子能谱图(XPS);[0022] 图8为对纯SR表面的分子结构和化学键进行检测的傅立叶红外光谱图(FTIR);[0023] 图9为对实施例1所得的HA-SR材料表面的分子结构和化学键进行检测的傅立叶红外光谱图(FTIR);[0024] 图10为对实施例2所得的HA-SR材料表面的分子结构和化学键进行检测的傅立叶红外光谱图(FTIR);[0025] 图11为培养在玻片上的对照组成纤维细胞的骨架分布图;[0026] 图12为培养在SR上的成纤维细胞的骨架分布图;[0027] 图13为培养在实施例1所得HA-SR上的成纤维细胞的骨架分布图;[0028] 图14为培养在实施例2所得HA-SR上的成纤维细胞的骨架分布图。 BRIEF DESCRIPTION [0014] accompanying drawings and the following embodiment of the present invention is further described: [0015] Figure 1 a schematic view of the structure according to the present invention is a silicone rubber light hydroxyapatite composites; [0016] FIG. 2 is Pure SR SEM microscopic topography (SEM) to observe the material; [0017] FIG. 3 is an observation of the resulting HA-SR coating material by scanning electron microscopy (SEM) morphology diagram of an embodiment; [0018] Figure 4 is observed with a scanning electron microscope (SEM) micro topography of the coating material obtained in Example 2 of HA-SR; [0019] FIG. 5 is a surface of the component of pure SR analysis of X-ray photoelectron spectrum (XPS) ; [0020] FIG. 6 for the component material of the surface of the HA-SR obtained in Example 1 was carried out the analysis of X-ray photoelectron spectrum (XPS); [0021] FIG. 7 is an embodiment of the HA-SR obtained surface 2 The composition analysis of X-ray photoelectron spectrum (XPS); [0022] FIG. 8 is a molecular structure and chemical bonding of the surface of pure SR detecting a Fourier transform infrared spectra (FTIR); [0023] FIG. 9 is for Example molecular structure and chemical bonding surface of the HA-SR 1 for detecting the resulting FTIR spectra (FTIR); [0024] FIG. 10 for the implementation of the molecular structure and chemical bonding HA-SR surface of the material obtained in Example 2 for detecting a Fourier IR spectra (FTIR); [0025] FIG. 11 is cultured on a glass slide control skeleton profile fibroblasts composition; [0026] FIG. 12 is a skeleton profile culture fibroblasts on the SR; [0027] FIG. 13 is a skeleton profile cultured fibroblasts obtained in Example 1 on HA-SR implemented; [0028] FIG. 14 is a skeleton profile cultured fibroblasts obtained in Example 2 of HA-SR. 具体实施方式[0029] 实施例1,本实施例中的硅橡胶一羟基磷灰石复合材料,如图1所示,包括硅橡胶层Ia和羟基磷灰石涂层lb,硅橡胶层Ia和羟基磷灰石涂层Ib通过硫化成型的方式制为一体结构;娃橡胶层Ia的厚度为0.5〜2mm,本实施例中具体取值为1.5mm ;所述轻基磷灰石涂层Ib的厚度为40〜150 μ m,本实施例中具体取值为40 μ m。 DETAILED DESCRIPTION [0029] Example 1, examples of a hydroxyapatite composite silicone rubber material of the present embodiment, shown in Figure 1, comprises a silicone rubber layer Ia and hydroxyapatite coating lb, and the silicone rubber layer Ia hydroxyapatite coating Ib way through vulcanization molding system as a whole structure; Ia baby rubber layer thickness 0.5~2mm, specific examples of the implementation of the value of 1.5mm; Ib and a light coating of hydroxyapatite having a thickness of 40~150 μ m, the specific values of the embodiment examples is 40 μ m. 该硅橡胶一羟基磷灰石复合材料的制备方法包括以下步骤:[0030] a、在温度为20C、湿度为50%的条件下,将双组份医用液态硅橡胶的A、B组分各取IOml混合,搅拌均匀后注入金属平板模具中,将其在-0.1MPa条件的真空泵中静置30min后取出;[0031] b、在温度20C的条件下静置硫化、固化5h后,将粒径为40 μ m的羟基磷灰石粉末均匀地喷涂于硅橡胶表面,静置30min后固化完全即可。 The preparation method of a hydroxyapatite composite silicone rubber material comprising the steps of: [0030] a, at a temperature of 20 C, humidity of 50% for the two-component liquid silicone rubber medical A, Group B points from each IOml mixed stir flat metal injection mold, allowed to stand in vacuum conditions -0.1MPa removed after 30min; [0031] b, at a temperature of 20 C curing conditions standing, solidified 5h After, the particle size of 40 μ m of hydroxyapatite powder uniformly sprayed on the surface of silicone rubber, can be completely cured upon standing 30min. [0032] 实施例2,与实施例不同的是,所述羟基磷灰石涂层Ib的厚度为150 μ m ;步骤b中采用粒径为40 μ m的羟基磷灰石粉末均匀地喷涂于硅橡胶表面。 [0032] Example 2 Example except that the thickness of the hydroxyapatite coating Ib is 150 μ m; step b, using 40 μ m particle diameter of hydroxyapatite powder uniformly sprayed on the silicone rubber surface. [0033] 上述两实施例中,步骤a中采用的金属平板模具可以采用长方体箱体结构,其尺寸要求可以为100mmX 100mmX 2mm、100mmX 100mmX Imm 或IOOmmX IOOmmX 0.5mm 三种型号。 [0033] the above-described two embodiments, step a mold used in the metal plate may be employed a rectangular parallelepiped box structure, the size requirements for 100mmX 100mmX 2mm, 100mmX 100mmX Imm or IOOmmX IOOmmX 0.5mm three models. [0034] 通过对上述两实施例所得的硅橡胶一羟基磷灰石复合材料进行各种检测,结果如下:[0035] 1、对于材料表面性能的评价,通过扫描电镜(SEM)观察涂层材料的微观形貌,SEM观察结果如图2、3、4所示,在100倍放大倍数下,纯SR表面平整、光滑、无杂质,实施例1所得的HA-SR材料表面可见大量粒径较小的羟基磷灰石颗粒,粘着紧密;实施例2所得的HA-SR材料表面粘着的羟基磷灰石颗粒粒径较大,与实施例1所得HA-SR材料相比,密度较低,但同样粘着紧密。 [0034] By the above-described two embodiments of a silicone rubber obtained hydroxyapatite composites of various testing, the results are as follows: [0035] 1, for the evaluation of the surface properties of the material, the coating material was observed by scanning electron microscopy (SEM) The morphology, SEM observation results shown in Figure 2, 3, at 100 times magnification, pure SR surface smooth, no impurities, HA-SR material surface obtained in Example 1 shows a large diameter than the small hydroxyapatite particles, sticking closely; larger HA-SR material obtained in Example 2 of the surface adhesion of hydroxyapatite particle size, as compared with Example 1 the resulting HA-SR material of Example, low density, but Also sticking closer. [0036] 2、对于材料表面的成分分析,由X射线光电子能谱(XPS)检测来完成,如图5、6、7所示,XPS检测结果:[0037] [0036] 2, the surface of the component analysis by X-ray photoelectron spectroscopy (XPS) to detect complete,, XPS test results shown in FIG. 6 and 7: [0037]

Figure CN102727933BD00051

[0039] XPS检测图谱显示,实施例1所得HA-SR材料与纯SR材料、实施例2所得HA-SR材料与纯SR材料相比,O、Si的百分比增加,C的百分比下降,其原因为实施例1的HA粒径小于实施例2的HA粒径,相比表面积增大,与SR形成了少量的化学键合,破坏了SR的-CH3键,导致C的百分比下降。 [0039] XPS spectra detected is displayed, the resulting HA-SR Example 1 and pure material of Example SR material obtained in Example 2 HA-SR SR material compared with pure material, O, Si percentage increases, the percentage of C decreases, the reason embodiment for the embodiment of Example 1 is less than the particle size of HA HA particle size in Example 2 embodiment, compared to the surface area increases, and the formation of a small amount of SR chemical bonding, the destruction of the SR -CH3 bond, resulting in decrease in the percentage of C. 同时,发现实施例1和实施例2所得的HA-SR材料中,Ca、P元素的对应点未出现明显波峰,证明HA未与SR形成明显的化学键合所致。 Meanwhile, due to co-found embodiment Example 1 and Example 2 obtained HA-SR materials, the corresponding point Ca, P element no obvious peaks, HA prove obvious chemical bond is not formed and SR. [0040] 3、利用傅立叶红外光谱(FTIR)对涂层材料表面的分子结构和化学键进行分析比较,如图8、9、10所示,结果如下:纯SR、实施例所得HA-SR材料和实施例2所得HA-SR材料中,-CH3> S1-O (-C)、-OH、C032_所对应的峰值无显著变化,说明HA与SR属于物理性结合,未破坏SR的官能团。 [0040] 3, using Fourier transform infrared spectroscopy (FTIR) molecular structure and chemical bonding surface coating materials were analyzed and compared, as shown in Figure 8, 9, results are as follows: pure SR, obtained in the example material and HA-SR Example 2 The resulting HA-SR material, -CH3> S1-O (-C), - OH, C032_ corresponding peak no significant change, indicating that HA and SR is the physical binding, undamaged SR functional groups. HA为磷酸钙的氢氧化合物,但实施例1和实施例2所得HA-SR材料中Ca2+、P043_的对应波形与SR相比差异不明显,可见HA与SR属于物理性结合。 HA calcium hydroxide compound, but the embodiment and the binding obtained in Example 2 material HA-SR Ca2 +, corresponding waveform P043_ obvious differences compared with SR, HA and SR are visible physical one. [0041] 4、利用激光共聚焦显微镜观察细胞骨架的结构图,如图11、12、13、14所示,可见微丝清晰,而材料上的细胞骨架确实发生了重排,有利于细胞的粘附。 [0041] 4, the use of laser confocal microscopy structure of the cytoskeleton, as shown in Figure 11,12,13,14 clearly visible filaments, while the material on the cytoskeleton rearrangement does occur, help cells adhesion. [0042] 最后说明的是,以上实施例仅用以说明本发明的技术方案而非限制,尽管参照较佳实施例对本发明进行了详细说明,本领域的普通技术人员应当理解,可以对本发明的技术方案进行修改或者等同替换,而不脱离本发明技术方案的宗旨和范围,其均应涵盖在本发明的权利要求范围当中。 [0042] Finally, note that the above embodiments are merely provided for describing the technical solutions of the present invention, not limitation, although reference to preferred embodiments of the present invention has been described in detail, those skilled in the art will appreciate, the present invention can be Technical Solution modifications or equivalent replacements without departing from the spirit and scope of the present invention, technical solutions, among which should be covered in the scope of claims of the present invention requires.

Classifications
International ClassificationA61L27/32, A61L27/18
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Oct 17, 2012C06Publication
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