CN102939125A - 用于区划血管治疗的装置和方法 - Google Patents
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Abstract
本发明公开了一种血管成形术气囊,所述气囊具有弹性限制结构,所述弹性限制结构与气囊一起部分膨胀,使得在最大气囊充气处,所述限制结构在气囊上形成沟道或“枕垫”图案。当气囊被充气使得抵靠所述部分施加的气囊膨胀的压力和程度被控制和限制时,这种不连续突起区域每一都单独地接合病变的一部分,从而在确保病变的所有部分被充分治疗的同时降低创伤的风险。
Description
本申请主张2010年3月12日提出的临时申请第61/313,600号(代理人号026728-000200US)的权益,该申请的全部公开内容通过引用在此并入。
技术领域
本发明涉及医疗方法和装置的领域,更具体地涉及用于将活性物质输送到人体组织的医疗血管成形术气囊导管和装置。
背景技术
血管成形术气囊是用于治疗狭窄血管的最常用的工具之一。这些气囊在被充气时通常为圆筒形并具有适应不同血管尺寸的不同长度和直径。气囊位于柔性导管的远端处并被输送给目标部位/病变,在所述目标部位/病变处,气囊在通常在8-20大气压之间的高压下被充气,以克服病变的阻力并获得内腔扩张。这种高压血管成形术通常与导致高频血管解剖(30%-40%)、治疗血管的急剧闭合(5%-12%)以及再狭窄的对血管壁的损伤相关联。因此,当传统的血管成形术用作阻塞血管的初级处理时,在大约50%的情况下可能会发生再狭窄。因此,在大多数冠状动脉治疗中,血管成形术用作放置支架之后的初步处理。经常,支架被涂布有使病人获取抗血小板治疗以持续长时间(可能是终生的)所需的药物和聚合物,以限制支架血栓或血块的风险。抗血小板治疗增加流血的风险并且是昂贵的。另外,在任何外科手术之前,病人必须停止抗血小板治疗,从而增加猝死的风险并经常阻止有益的方法。
由气囊血管成形术治疗血管的解剖是公知的。在所有案件中解剖率估计高达30%。一些解剖是严格的并且可能需要紧急外科手术或放置另外的支架。另外,即使将支架放置在被治疗的病变中,解剖也可能会导致较差的长期临床结果和再狭窄。解剖通常被归因于在气囊充气期间发生的包括当气囊褶展开时施加在血管壁上的剪切力的多种机理以及由于血管疾病的非对称特性而导致的不均匀的气囊充气。在充气期间,当皱折的气囊展开时,气囊直径在径向方向上增加。当气囊的皱折气袋打开时,层彼此滑过并将切向力施加到病变和/或血管壁,从而可以切除病变或血管壁,并且在最坏的情况下导致解剖。如图1A-1C所示,导管10被初始定位在血管(BV)中的血小板(P)的区域中。导管10上的气囊12具有皱折的气袋,当气囊被充气时,所述气袋展开,如图1B所示。皱折的气袋的多个层在相反的方向上移动,如由图1B中的箭头所示,且上暴露层往往滑动横过病变的表面,或者如果存在,则露出血管壁。直到气囊被完全充气,气囊表面的这种无意横向移动才不会发生,如图1C所示。
不均匀的膨胀由血管中的疾病的不平坦特性所导致。血管成形术气囊通常是非柔性的或半柔性的,并且当半柔性气囊抵靠偏心病变被充气时,气囊将沿着“最小阻力的路径”,并且气囊的直径将在血管的较少疾病部分增加得更多,从而通常增加这些区域中的损伤。
为此,期望提供一种用于在脉管治疗中使用的血管成形术气囊的改进的气囊和充气结构。具体地,期望提供通过调节气囊的充气特性来减小当气囊被充气时血管壁中的损伤和解剖的倾向性的血管成形术气囊,并且期望提供具有顺性局部区域的分区充气。如果减小的解剖将会降低与当前血管成形术气囊及其使用相关联的弹性反冲和急剧再闭合的风险,则这是进一步期望的。如果这种改进的血管成形术气囊结构与支架、药物洗脱支架以及药物涂层球囊兼容,则这是进一步期望的。这些优点将在不损失导管的性能的情况下被优选地获得,从而增加内腔尺寸并恢复正在被治疗的病人中的血管。这些目标中的至少一些由如下文所述的本发明来满足。
美国专利第6,245,040号和第5,735,816号显示了气囊导管,所述气囊导管具有当气囊被充气时在气囊中形成螺旋凹部的弹性螺旋限制器。感兴趣的其它专利包括美国专利第7,708,748号、第7,686,824号、第5,863,284号、第5,772,681号、第5,643,210号以及第5,987,661号。
发明内容
本发明包括一种用于血管成形术或狭窄血管的扩张以及任选地用于将活性物质输送到血管壁的装置。气囊导管被设计成调节气囊的膨胀特征,从而为分割的区划扩张提供能够使血管疾病的不均匀性质一致的局部区域柔量。本发明的气囊导管包括限制结构(CS),所述限制结构位于导管的远端上的气囊上。CS用于通常通过在血管的小区域中产生局部扩张的表面上形成突起区域(“枕垫”)(与由相邻的突起区域形成的无关)来控制和限制气囊充气并改变气囊构形。当气囊被充气使得克服所述部分施加的压力和气囊膨胀程度被控制和限制时,这种不连续突起区域中的每一个都独立地接合病变的一部分,从而在确保病变的所有部分被充分治疗的同时降低创伤的风险。病变可以沿着其长度被均匀地治疗,同时可以降低或整体避免在病变的任一部分施加过分的压力。这种局部扩张避免上述“最小阻力路径”现象并允许对血管的不同部分或区域进行局部和非均匀治疗,其中当气囊被充气到与血管形成术相关联的超高压时,被改变的气囊构形使血管壁的创伤和损伤最小化。当气囊充气并且壁层打开并相对于血管壁横向滑动时,CS还抑制剪切力到病变和血管壁的传递。传统的气囊具有横过血管的治疗部分的连续表面(有时在神经末梢损害中只要200mm至300mm即可),从而导致气囊沿着治疗部分变形以及不平坦。这种“聚合扩张”机构当施加到具有不均匀病变几何结构的病变血管时会增加创伤和解剖的概率。相反,即使当病变的尺寸在其长度上显著变化时,本发明的气囊沿着病变的长度提供更加局部化但被平衡的力分布(例如,由于均匀分布的突起区域)。
在本发明的一个实施例中,CS位于收缩并皱折的气囊上并靠近气囊的远端、靠近气囊的近端或优选地靠近气囊的远端和气囊的近端连接到导管的轴。CS无须连接到气囊并且可以在皱折气囊上浮动,其中所述气囊任选地具有在任一端或两端处具有弹性罩(例如,由聚合物制成的罩)。在气囊充气时,CS膨胀到其最大直径并允许气囊通过CS中的开口以预先选定的图案进一步膨胀。在装置收缩时,CS将弹性接近其初始直径。
在本发明的一个实施例中,当气囊充气时,气囊和CS的直径都增加。然而,CS的最大打开直径小于完全被充气的气囊直径,因此,气囊通过CS中的开口继续膨胀,从而产生一连串突起区域,通常为正交或菱形“绗缝”图案。CS具有在膨胀之前具有相对较小的直径,并且由于由气囊膨胀施加的充气力而能够膨胀到小于完全被充气的气囊的直径的直径。CS膨胀受到其结构设计的限制。
CS被设计成在充气过程期间以消除大直径差的方式通过限制和约束横过治疗部分的气囊直径来控制气囊充气。因此,当气囊压力增加时,与通常做法一样,以便克服局部狭窄,可以整体上减小或避免过度拉伸被治疗病变的其它部分。另外,CS可以减小或消除由气囊抵靠血管壁展开而产生的切向力的传递。CS产生由交叉沟道与在交叉沟道之间的突起区域或“枕垫”形成的网格。突起区域之间的沟道通过在邻近突出区域之间提供应力消除来防止高径向应力增长。应力消除区域在不会与气囊表面直接接触的情况下可以伸展或扩大,因此使在充气期间对血管壁的创伤最小化。另外,沟道允许血小板挤出(重新分配),从而除了传统的气囊的简单压缩机构之外增加新机构。
在第一方面中,本发明提供一种用于执行血管成形术的系统。所述系统包括导管轴和限制结构,所述导管轴在其远端处具有可充气气囊,所述限制结构设置在可充气气囊上。限制结构具有非膨胀结构和膨胀结构,在所述非膨胀结构中,限制结构在充气之前紧密地位于气囊的皱折上或位于气囊的皱折内,在所述膨胀结构中,限制结构小于未受限制的气囊的尺寸(当完全充气时),使得所述结构沿着多个交叉沟道线限制气囊充气。通过“交叉”沟道线,这意味着沟道在多个位置处相交,使得沟道包括由相互连接的沟道形成的相交矩阵。各个沟道线可以轴向地、沿圆周方向定向,或者优选地包括具有轴向定向和周向定向的沟道线,其中轴线沟道与周向沟道相交。可选地,沟道可以被形成为相交以形成菱形突起区域的两个或更多个反向缠绕的螺旋形沟道。
在具体的优选实施例中,限制结构包括多个沿圆周方向间隔开的轴向柱和连接到轴向柱的多个轴向间隔开的径向可膨胀环。环以优选地在从大约75度到105度的范围内的相交角度连接到柱。在尤其优选的实施例中,相交角度为90度。轴向柱在气囊的远端侧和气囊的近端侧连接到导管。在一些实施例中,当气囊被充气(以适应否则可能会出现的缩短)时,远端柱端部和近端柱端部中的至少一个在导管轴上自由轴向平移。可选地,各个柱可以在气囊的近端侧和远端侧固定地连接到导管轴,其中柱是弹性的或者以其它方式可拉伸,使得当气囊被充气时所述柱拉伸。例如,轴向柱可以由弹性体或允许拉伸的其它弹性材料构成。更通常地,轴向柱包括当柱端部中的任一个或两个连接到导管轴时适应拉伸(如果需要)的诸如Z字形、S形连接、螺旋弹簧等的特征。
径向可膨胀环还被形成为使得当气囊在环中被充气时径向可膨胀环可以延伸或拉伸以增加直径。可膨胀环可以由诸如可拉伸聚合物等固有的弹性材料形成,然而更通常形成有当气囊被充气时允许环膨胀的可膨胀特征。可膨胀特征可以与轴向柱相同。
气囊还可以被涂布或以其它方式适于输送药物。用于使气囊涂布有药物的在专利文献中被详细描述。例如,参见US7,750,041、US2010/02280228、US2010/0278744、以及US2008/0102034,所述申请的全部内容通过引用在此并入供参考。
在第二方面中,本发明提供一种用于治疗血管中的病变的方法。所述方法包括以下步骤:使气囊在血管内充气,其中气囊沿着多个交叉沟道线受到限制,所述交叉沟道线通常为彼此相交和交叉的轴向和/或周向沟道线。沟道线在气囊中产生多个间隔开的突起区域,其中突起区域接触病变,同时沟道线远离血管壁凹入。“凹入”表示沟道线的底部或凹部被径向定位成相对于气囊的充气表面更加靠近导管的轴线。在很多情况下,沟道的底部不会接触病变或血管壁。然而,在其它情况下,尤其当血小板或血栓被挤压时,由于沟道的底部保持与血管壁径向向内间隔开,因此沟道可以填充有病变物质,同时提供上述应力消除的益处。
气囊通常由非膨胀或半柔性材料构成,使得所述气囊可以在相对较高的压力(通常在从10个大气压到25个大气压的范围内)下在血管内膨胀。因此,当气囊在最大直径差值限定形成在气囊表面中的沟道的深度的情况下被完全充气时,气囊(当是不可膨胀的时)和限制结构将具有最大直径。突起区域通常具有类似的尺寸(±50%的区域接合病变)并在气囊表面上均匀分布。气囊可以用于血管成形术,且不需要随后的支架输送和/或药物输送。可选地,气囊可以用于支架,包括涂药支架和没有被涂布的支架。最终地,气囊本身可以在治疗期间涂布有药物以将药物输送到病变或血管壁。
附图说明
图1A-1C显示了在狭窄的血管中的传统的气囊充气的展开阶段的横截面;
图2A、2B1和2B2显示了在充气之前(图2B1)和充气之后(图2A和2B2)位于气囊上的限制结构;
图3A和3B显示了其中相邻轴向柱之间的环形片形成为Z字形图案的第一示例性环状结构;
图4A和4B显示了其中相邻轴向柱之间的环形片形成为S形图案的第一示例性环状结构;
图5A和5B显示了其中相邻轴向柱之间的环形片形成为线圈弹簧的第一示例性环状结构;
图6A-6C显示了在气囊在限制装置中展开的情况下本发明的充气装置在充气的三个阶段期间的横截面;以及图7A和7B显示了传统的气囊和本发明中所述的装置的血管损伤的有限元分析。
具体实施方式
本发明提供了一种用于治疗身体内的病变、堵塞、阻塞或狭窄内腔的装置,典型地血管包括动脉和静脉,并且更典型地包括冠状动脉和周围动脉。该装置在使对病变和内腔壁的损伤最小化并降低血管损伤和损害的风险的同时扩张阻塞的血管。通过将“弹性”限制结构(CS)放置在气囊导管的气囊上,气囊的充气在气囊充气期间被控制,并且当气囊收缩时有助于气囊的再次褶皱。CS被设计成当被完全充气时膨胀到小于气囊的最大直径的直径。CS结构将径向阻力施加给充气装置并因此能够限制气囊并分配或缓冲由气囊施加到内腔壁的内部高压,从而提供一种受控制的且小创伤的充气方法。典型地由诸如聚酰胺或聚醚嵌段酰胺的非膨胀材料形成的气囊优选地是不可膨胀的或半柔性的,且具有在典型的充气压力范围内的10%以下的拉伸性以及充分大的完全充气尺寸,使得区域通过CS中的通道突起以形成接合和扩张病变的突起区域。
CS可以被联接或以其它方式被连接到在气囊的远端侧和/或近端侧上的导管轴。可选地,CS可以在不需要固定连接的情况下使用简单的罩或限制装置在气囊上浮动,并且CS优选地被设计成在气囊的膨胀期间保持其长度以限制CS与气囊之间的相对轴向运动。CS可以由各种材料使用适当的方法和设计被制造而成。CS可以由金属制成,优选地由诸如镍-钛合金(Nitinol(R))的弹性金属制成和/或由各种聚合物(例如,尼龙)制成。例如,CS可以由线构造而成,或者可以从管、鞘或其它材料形式被激光切割。
在本发明的优选实施例中,CS结构位于气囊上并在气囊充气期间膨胀。CS膨胀到小于气囊的直径,因此将气囊充气限制在圆筒形笼中。然而,在CS产生被控制的扩张图案并减小或消除剪切力的情况下,气囊的多个部分通过开口保持膨胀。
一旦CS达到其最大直径(该最大直径小于最大充气气囊直径),气囊通过CS中的开口继续膨胀,从而在装置的表面上产生由突起区域(丘陵)和沟道(山谷)形成的形式,其中沟道的图案由CS的几何结构限定。CS促成被控制的膨胀过程,从而避免过度膨胀并最小化施加在血管壁上的剪切力和均匀的高压,如以下参照图6A-6C和图7更加详细地说明。
以下参照图2A、2B1和2B2,根据本发明的原理构造而成的示例性限制结构14包括多个轴向柱16和轴向分隔开的径向可膨胀环18。当气囊12和导管10处于非充气状态(如图2B1所示)时,气囊被皱折有多个重叠的气袋,如图6A中最清楚地所示(以下所述)。限制结构14具有大致圆筒形几何结构,所述圆筒形几何结构具有正好大到足以遮盖收缩的气囊12的直径。
当气囊12被充气时,如图2A和2B2所示,径向可膨胀环18响应于气囊的力膨胀。然而,环将被构造成使得所述环达到该环不再径向膨胀的最大直径,而与气囊的继续充气或膨胀无关。当轴向柱16连接或以其它方式联接到径向可膨胀环18时,柱的径向向外行程还受限于由环的最大直径限定的距离。因此,由于气囊具有大于径向可膨胀环18的最大直径的完全充气直径,因此当气囊被完全充气时,多个轴向以及周向沟道20和22将分别形成在气囊表面中。多个突起区域24(如图2B中所示)限定在相邻的轴向柱16与径向可膨胀环18之间的开口或空隙中。这些突出区域24提供如上所述的本发明的益处。
限制结构14的轴向柱16和径向可膨胀环18被示出为简单的平直梁或元件,要理解的是轴向柱16和径向可膨胀环18需要具有一些弹性或拉伸性以适应气囊的径向膨胀和环的尺寸的径向增加。虽然由于轴向柱14可以沿着近端和远端处的导管轴26自由滑动,因此仅需要使轴向柱14是柔性的,尽管如上所述环具有超过环不再膨胀的最大直径,但是环18必须能够在气囊的直径增加时在周向尺寸上拉伸。最简单地,轴向柱16和/或径向膨胀环18可以由能够在拉力下拉伸的诸如弹性聚合物、线圈弹簧等的弹性材料形成。此外,如果这些材料和/或结构与径向可膨胀环一起使用,还必须具有用于径向膨胀限制的单独的不可膨胀或不可拉伸部件。
可选地,轴向柱16和/或径向可膨胀环18可以由大致不可拉伸材料形成,典型地为诸如上述镍钛合金的金属形成,并且设有允许在拉力下拉伸的特征或图案。例如,如图3A和3B所示,径向可膨胀环18可以形成为Z字形图案,使得所述径向可膨胀环18可以从如图3A所示的短小结构拉伸到如图3B所示的完全拉伸结构。虽然未示出,但是要理解的是轴向柱可以采用允许轴向拉伸的相同的几何特征。图4A和4B示出了环18可以设有允许从短小结构(图4A)拉伸到对应于图2A和2B2所示的完全膨胀后的直径结构的完全拉伸结构(图4B)的S形或蛇形结构。可选地,环18可以设有线圈结构,如图5A和5B所示,其中当环处于其最小直径时,线圈呈现出短小结构,如图5A所示,并将伸展以适应完全展开结构,如图5B所示。然而,类似于上述的弹性聚合物实施例,线圈弹簧将在大多数情况下需要防止超过期望的最大限制的膨胀的单独元件或部件。
以下参照图6A-6C,携带气囊12和限制结构14的导管10以通常传统的方式被引入到血小板P和血管BV的区域中。一旦气囊12和限制结构14处于目标位置,气囊被充气,从而使限制结构14径向膨胀直到该限制结构达到最大直径为止,如图6B所示。一旦限制结构14已经到达其最大直径,限制结构14将不再膨胀,但是气囊12的位于相邻轴向柱与径向可膨胀环之间的打开区域中的部分将继续膨胀,直到达到其最大膨胀为止,如图6C所示,其中充分形成的突出区域出现。由于气囊12典型地由不可膨胀材料形成,如上所述,一旦已经达到最大气囊尺寸,进一步的气囊充气将不会明显增加气囊尺寸。
图7A和7B显示了施加在血管壁上的力的有限元分析,从而比较传统的气囊(图7A)与本发明的装置(图7B)。与本发明的在组织不与气囊接触的区域中显示拉伸的气囊相比较,传统的气囊显示均匀的高应变。均匀的气囊压力被减少血管损伤的交替压力图案替换。
可以使用本发明输送各种试剂或活性物质,所述各种试剂或活性物质尤其适于(但不限于)治疗脉管和其它内腔状态,例如,抗恶性细胞增生和抗有丝分裂剂(例如,紫杉醇和西罗莫司)。其它物质可以包括抗菌素、抗血小板剂激素以及更多。
活性物质可以被放置在各种设计或技术中,例如直接涂布在气囊表面、CS或气囊表面和CS上。活性物质可以被植入设置在气囊或CS或气囊和CS上的基体/携带体中。对于一些部分来说,低损伤扩张与活化剂的释放的组合通过使对永久植入的需要最小化而优于药物洗脱支架,但是仍然提供良好的长期结果。
在一个实施例中,气囊表面被涂布有药物。在气囊充气时,形成在涂布有药物的气囊外表面中的突起区域接合血管壁并将药物挤压到壁中以有助于将药物输送到治疗部位。
可以使用许多不同的设计方法,包括但不限于涂布气囊、涂布CS结构、或涂布气囊和CS结构,而使得药物输送更加方便。直接涂布药物或使用基体或微胶囊形式的携带体。
虽然以上是本发明的优选实施例的完整描述,但是各种可选形式、修改、添加和替换在不背离本发明的由权利要求限定的保护范围的情况下是可以的。
Claims (23)
1.一种用于执行血管成形术的系统,所述系统包括:
导管轴,所述导管轴在其远端处具有可膨胀气囊;
限制结构,所述限制结构设置在所述可膨胀气囊上,所述限制结构具有非膨胀结构和膨胀结构,在所述非膨胀结构中,所述限制结构在充气之前紧密地位于所述气囊上,在所述膨胀结构中,所述限制结构小于所述气囊的不受限制的尺寸,使得所述结构沿着多条交叉沟道线限制气囊充气。
2.根据权利要求1所述的系统,其中,所述沟道线沿圆周方向轴向地定向,或者在轴向上并沿圆周方向定向。
3.根据权利要求2所述的系统,其中,所述限制结构包括多个沿圆周方向分隔开的轴向柱和连接到所述轴向柱的多个轴向分隔开的径向可膨胀环,其中所述轴向柱与径向可膨胀环交叉。
4.根据权利要求3所述的系统,其中,所述环以在75度到105度的范围内的相交角度连接到所述柱。
5.根据权利要求4所述的系统,其中,所述相交角度为90度。
6.根据权利要求3所述的系统,其中,所述轴向柱在所述气囊的远端侧和所述气囊的近端侧连接到所述导管。
7.根据权利要求6所述的系统,其中,当所述气囊被充气时,每一个柱的远端和每一个柱的近端中的至少一个能够在所述导管轴上轴向平移。
8.根据权利要求6所述的系统,其中,各个所述柱的每一个都能够弹性拉伸,使得当所述气囊被充气时所述柱拉伸。
9.根据权利要求8所述的系统,其中,每一个结构的两端都被固定地连接到所述导管轴。
10.根据权利要求3所述的系统,其中,所述径向可膨胀环由弹性材料构成,当所述气囊被充气时,所述弹性材料能够拉伸以允许所述环膨胀。
11.根据权利要求10所述的系统,其中,所述径向可膨胀环形成有可变形特征,当所述气囊被膨胀时,所述可变形特征允许所述径向可膨胀环径向膨胀。
12.根据权利要求11所述的系统,其中,所述可变形特征包括Z字形、S形曲线和线圈中的一个或多个。
13.根据权利要求1所述的系统,其中,所述气囊被涂布有要被输送到血管壁中的药物。
14.一种用于处理血管中的病变的方法,所述方法包括以下步骤:
使气囊在所述血管内充气;以及
沿着多个交叉沟道线限制所述气囊充气,其中当所述沟道线从所述血管壁凹入时,多个间隔开的突起区域接触所述病变。
15.根据权利要求13所述的方法,其中,所述气囊由非膨胀或半柔性材料构成,并且被膨胀到从10个大气压到25个大气压范围内的压力。
16.根据权利要求13所述的方法,其中,所述气囊沿着交叉的轴向和周向沟道线受到限制以形成四边形的间隔开的突起区域。
17.根据权利要求13所述的方法,其中,所述气囊被涂布有药物,当所述气囊被充气时,所述药物被输送到所述血管壁。
18.一种用于治疗血管中的不均匀病变的方法,所述方法包括以下步骤:
使气囊在所述病变中充气,其中所述气囊表面被形成为多个不连续的突起区域,所述突起区域的每一个都使所述病变的一部分与由每一个突起区域施加的局部化力单独地接合,以避免在所述病变的任意部分上施加过分压力。
19.根据权利要求18所述的方法,其中,所述突起区域由限制结构形成,所述限制结构具有设置在所述气囊上的交叉柱。
20.根据权利要求19所述的方法,其中,所述柱沿着轴向和周向线设置以形成四边形的间隔开的突起区域。
21.根据权利要求18所述的方法,其中,所述气囊由非膨胀或半柔性材料形成并且被充气到从10个大气到25个大气压的范围内的压力。
22.根据权利要求18所述的方法,其中,所述气囊被涂布有药物,当所述气囊被充气时,所述药物被输送到所述血管壁中。
23.根据权利要求18所述的方法,其中,所述突起区域具有类似的尺寸并且在所述气囊表面上均匀分布。
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Also Published As
Publication number | Publication date |
---|---|
JP2013521937A (ja) | 2013-06-13 |
CN102939125B (zh) | 2015-12-16 |
SG184038A1 (en) | 2012-10-30 |
EP2544752B1 (en) | 2020-09-23 |
US10549077B2 (en) | 2020-02-04 |
US11529500B2 (en) | 2022-12-20 |
US20200215311A1 (en) | 2020-07-09 |
EP2544752A4 (en) | 2013-11-27 |
WO2011112863A1 (en) | 2011-09-15 |
US20160074634A1 (en) | 2016-03-17 |
SG10201501117PA (en) | 2015-04-29 |
US9199066B2 (en) | 2015-12-01 |
US20120059401A1 (en) | 2012-03-08 |
JP5955310B2 (ja) | 2016-07-20 |
EP2544752A1 (en) | 2013-01-16 |
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