TW201438593A - 製備具有增加的燕麥蒽醯胺含量之高度可分散全穀物粉之方法 - Google Patents
製備具有增加的燕麥蒽醯胺含量之高度可分散全穀物粉之方法 Download PDFInfo
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Abstract
一種製備高度可分散全穀物燕麥粉的方法,該方法係藉由水解、研磨及凝聚穀物粉,以得到相較於天然的燕麥粉具有增加的燕麥蒽醯胺含量之全穀物燕麥粉。
Description
本申請案主張2013年3月15日提申之U.S.專利申請案號13/833,717的優先權,其揭示內容以參照方式明確地併入本案。
本發明大致上關於製備高度可分散或者稱作“可溶性”全穀物粉的方法。更明確地說,本發明係關於製造具有增加的燕麥蒽醯胺含量之高度可分散燕麥粉的方法。
由於顧慮到高膽固醇、肥胖和心臟疾病,很多消費者有興趣就自己的飲食做出更健康的選擇。為此,存在提供消費者全穀物、低膽固醇產品的需求。然而,隨著快節奏的生活方式,消費者很難準備健康的膳食或點心。因此,亦存在提供消費者即食營養產品的需求。再者,市場上存在有以可飲用形式含有高位準全穀物之可食用品項的
需求。
所欲的是製備在處理期間保持其結構(即澱粉質胚乳、胚芽與糠麩)以滿足證明健康聲明所必要的FDA門檻的全穀物產品。更明確地說,所欲的是製備在處理期間保持全穀物結構、高度可分散於液體或半固體介質之水解全穀物粉。
食品工業已嘗試提供在整個處理過程當中保持其全穀物結構之水解全穀物;然而,水解全穀物粉容易結塊,有無法接受的口感且/或對消費者沒有吸引力。本發明克服前述問題並提供消費者保持其全穀物結構與營養價值、高度可分散於液體或半固體介質之水解全穀物粉,藉此具有改良口感並提高消費者的接受度。
燕麥蒽醯胺為燕麥獨有的抗氧化劑。自從其於1980年代首次單離迄今,已鑑定出超過30個同系物,燕麥中最豐富的燕麥蒽醯胺為2p、2f與2c。該等多酚驗證了強力的抗氧化、抗發炎與抗動脈粥樣硬化特性,並可有益於患有慢性發炎疾病、過敏和心血管疾病的人們。在食品工業以外,燕麥蒽醯胺的益處亦有據可查。利喘貝(Tranilast)-燕麥蒽醯胺相似物-已被批准用於治療發炎相關疾病以及護膚產品AveenoTM係依據燕麥蒽醯胺之經證實益處。
為了達到對人體健康的有益效應,燕麥蒽醯胺必須被足量攝取。在1999年塔夫茨大學的研究當中,確認了燕麥蒽醯胺在攝取後於人體中具有生物利用性且仍具有生物活性。在服用60或120mg後,總血漿燕麥蒽醯胺的最大
濃度分別為168與560nM。由明尼蘇達大學進行的較近期研究顯示,歷時8周服用低至每日0.4或9.2mg劑量之燕麥蒽醯胺增加了血漿總抗氧化活性且對數種抗氧化與抗發炎參數具有劑量-回應效應。該等效應或許是由於燕麥蒽醯胺在不同組織與器官中的累積與高濃度所致。
在燕麥穀物中的燕麥蒽醯胺含量係依品種與食物處理方法而異。舉例來說,熱處理通常減少了燕麥蒽醯胺2f、2c,更大大地減少了2p。增加燕麥蒽醯胺含量的處理方法是非常重要的,以幫助人們透過經常食用燕麥產品達到健康益處。
核因子-κB(NF-κB)是調節DNA轉錄的一個真核轉錄因子家族並涉及發炎與免疫反應相關基因的活化。NF-κB所調節的發炎反應係經由增強編碼有致發炎細胞激素-例如腫瘤壞死因子(TNF)-α、白細胞介素(IL)-6、及白細胞介素(IL)-1β-的基因表現來發生。NF-κB的活化導致發炎,其轉而涉及許多疾病的發病機制,例如氣喘、類風濕性關節炎、及發炎性腸病且至少部分地為諸如動脈粥樣硬化與阿茲海默症之疾病的致病原因。壓制NF-κB-對感染之免疫反應的調節劑-是限制腫瘤細胞增殖的關鍵並減少發炎位準。研究已顯示燕麥蒽醯胺抑制NF-κB活化。
本發明之態樣係關於具有增加的燕麥蒽醯胺含量之可溶性燕麥粉。本發明之另外態樣係關於製備水解全
穀物粉的方法。在本發明一態樣中,酶係於保持全穀物完整性的同時水解全穀物粉。
在本發明另一態樣中,全穀物係經研細並接著凝聚,以增進穀物於液體與半固體介質中的可分散性。用於凝聚的穀物可未經處理/天然的、預膠凝化、或經水解。
該等及其他態樣-連同本案所揭示之本發明優點與特徵-將透過參照下列說明與隨附圖式而變得顯明。而且,欲被理解到的是本案所述各式具體例的特徵並非相互排斥而是可存在各式組合和置換。
本發明之眾多其他目的、特徵及優點將由下列圖式說明顯而易見。
圖1例示玉米及根據本發明製備之全麥粉的擠壓前與擠壓後之澱粉值比對。
圖2例示經由擠壓處理前後及經由擠壓與加酶處理前後之全燕麥粉樣本之澱粉含量比對。
圖3A係比對使用本案所述方法形成之全燕麥粉(“SoluOats”)中所發現的燕麥蒽醯胺位準(2C、2P、2F及該等燕麥蒽醯胺的總位準)。
圖3B係比對使用本案所述方法形成之全燕麥粉(“SoluOats”)中所發現的燕麥蒽醯胺位準(2C、2P、2F及該等燕麥蒽醯胺的總位準)。
圖4係比對從表2所列示各式處理條件得到的燕麥粉中所識別的燕麥蒽醯胺份量。
圖5繪示在全燕麥粉、本案所述方法(“SoluOats”)、及空白組中的NF-κB抑制活性之變化百分比。
本發明係關於一種超越根據先前習知方法所製備可溶性燕麥粉之具有增加的燕麥蒽醯胺位準之可溶性燕麥粉。尤其,本發明係關於一種製備高度可分散全穀物粉的方法,又,本發明係關於一種在整個處理過程當中保持其全穀物狀態並高度可分散於液體與半固體介質中的水解全穀物粉。全穀物可為任何適宜的穀類穀物,例如燕麥、小麥、玉米(玉蜀黍)、稻米、大麥、黑麥、藜麥、高粱、小米、黑小麥,或該等之組合。如本案所列示,“全穀物狀態”、“全穀物識別標準”、“如同全穀物之識別標準”或“保持全穀物完整性”應指由完整、碾磨、壓碎、薄片狀穎果所構成之全穀物的主要解剖組份-澱粉質胚乳、胚芽與糠麩-係以如同該等存在於完整穎果中的相同相對比例存在。粉的可分散性係於水中測量,待攪拌五(5)秒後觀察硬塊的形成與硬塊的尺寸以及形成在水的頂部與底部上的硬塊。就根據本揭示內容製得的粉而言,在攪拌混合物約五(5)秒後,沒有硬塊出現或形成。
在本發明一態樣中,水解全穀物粉的方法包括水解、研磨、及凝聚全穀物粉。更明確地說,該粉係使用酶來水解。根據本發明所使用的酶容許全穀物粉保持其作為全穀物的識別標準。在保持全穀物完整性的同時水解全穀
物粉之酶的一個例子為阿伐澱粉酶。根據本發明所使用的酶可為水解構成全穀物澱粉部分之支鏈澱粉分子上的阿伐1-4鍵的任何酶。該酶亦可水解全穀物的直鏈澱粉分子。適宜的酶包括介於約0.01-0.5%範圍,舉例來說,約0.1-0.2%之α-澱粉酶。在本揭示內容一態樣中,所使用的α-澱粉酶可為具有大約1,000,000MWU/g(MWU-改質伍氏單位(Modified Wohlgemuth Unit))的Validase BAA 1000L。具食品科學領域通常知識者將認知到根據本發明可使用一或多個酶。全穀物粉-例如使用本案列示方法之小麥粉與燕麥粉-的測試與分析已核實並確認在整個處理過程當中保持了澱粉分子。此測試結果係例示於圖1與2。如下表1顯示,根據本發明此態樣製得的食物成分的任何變化最佳可忽略不計。
藉由在整個處理過程當中保持全穀物的狀態,“全穀物”健康聲明可由根據本發明製得之水解全穀物粉做到。再者,在整個處理過程當中保持了全穀物的營養主幹;
因此,藉由本案列示方法製造的水解全穀物粉提供了如同未水解全穀物粉的相同營養益處。
在本發明一態樣中,乾燥全穀物粉係藉由以水與蒸汽使全穀物粉起始混合物水合至約30%之整體水份(dw)來進行預調理。隨後將在保持全穀物完整性的同時水解全穀物粉的至少一酶加至該混合物。在本發明另一態樣中,乾燥全穀物粉可混合有糖、麥芽糊精及/或混合生育醇。
在使全穀物粉水合一段適宜時間量後,隨後將經酶處置之混合物投至擠壓方法,以繼續裂解及水解全穀物粉,並膠凝化及烹煮混合物,以形成烹煮過的水解全穀物麵團。使該混合物滯留於擠壓機中一段足以膠凝化及烹煮澱粉、但沒長到足夠讓澱粉糊精化至不再是全穀物的程度或以其他方式改質而破壞全穀物樣態的時間,大致上至少1分鐘,通常為約1至約1.5分鐘。大致上,該材料係自起始入口溫度加熱至最終出口溫度,以提供用於澱粉膠凝化的能量。在本發明一態樣中,在烹煮擠壓機出口的麵團壓力係約900-1000psi。在離開烹煮擠壓機之前,該麵團係加熱至約260-300℉,舉例而言,約265-285℉,以讓酶完全失活。
澱粉的膠凝化需要水和熱量。燕麥的膠凝化溫度範圍為127℉至138℉(53-59℃)。假使水份少於約60%,則需較高溫度。
熱量可透過擠壓機筒壁,例如藉由循環有像是蒸汽、水或油之熱介質之包圍筒身的套件、或埋置在筒身內
的電熱器來施加。通常,擠壓發生在介於140℉與350℉之間,舉例來說,介於175℉與340℉之間、更明確地約180℉-300℉之筒身溫度。
隨著藉由擠壓機中所損耗的機械能使得材料在擠壓機內移動,熱量亦藉由摩擦而產生在材料之內,就牛頓流體而言,其等於黏度與剪切率平方的乘積。剪切係由(多個)擠壓機螺桿的設計與螺桿速度所控制。黏度為澱粉結構、溫度、水份含量、脂肪含量與剪切的函數。麵團溫度在擠壓機中係增加至大約212℉與300℉。
低剪切係施加至擠壓機中的混合物。隨著酶已將澱粉預調理至約30%水份,此方法並不需要高剪切。高剪切亦可能過度增加麵團溫度,可能讓麵團煮過頭而導致過多的烹煮穀物氣味。要注意的是筒身溫度與麵團溫度可不同。
該方法在限制麵團溫度以避免過多的烹煮穀物氣味以及維持酶的活性之間取得平衡。該方法已達平衡,使得麵團溫度升高至足以讓酶失活的溫度。該溫度為至少280℉,大致上為212℉至300℉。熟習此藝者將理解到用來讓酶失活的溫度係取決於酶維持在此溫度的時間。低剪切擠壓方法相較於高剪切擠壓之特徵係為高水份與低剪切螺桿設計相對於低水份與高剪切螺桿設計。
可使用任何適宜的擠壓機,包括適宜的單螺桿或雙螺桿擠壓機。典型但非設限的螺桿速度為200-300rpm。具本領域通常知識者將認知到的是,螺桿速度係取決於螺
桿設計。
所得產物可使用成型擠壓機造粒並乾燥。在本發明一態樣中,該方法從預調理步驟到通過擠壓機與成型擠壓機耗時約9-10分鐘。而且,該丸粒可研細至約50-200微米。可用來研細丸粒的一類研磨方法係包括漸減式輥磨處理法。該丸粒可在研磨前乾燥至約8±2%水份。最終,研細的水解穀物粉可凝聚至約150-700微米。丸粒之研細動作改善了所得水解燕麥粉的口感且因此提高了所得產品的消費者接受度。
研磨後的凝聚步驟係有利在於最佳化並大大地改善分散性且其適用於製備可食產品之許多應用。在本發明一態樣中,微細全穀物顆粒係使用2%糖黏結劑溶液凝聚。舉例來說,凝聚化水解穀物粉可加至、且高度可分散於液體與半固體介質中,例如水、奶、果汁、優格、布丁及其他可飲用點心形式。又,根據本發明製得的凝聚化水解穀物粉容易讓消費者輕鬆並有效率地使用普通家用餐具將粉攪進他們所選擇的液體或半固體裡,因為該水解穀物粉可快速分散於該等液體或半固體。又,根據本發明製得的凝聚化水解穀物粉可藉由簡單地搖動來混合組份而分散於液體介質內。
在本發明一實施例中,根據本發明製得的凝聚化水解燕麥粉展現了下表2所標識的特性:表2
在本發明另一態樣中,未處理/天然的全穀物係研細至約50-420微米,例如約50-200微米之顆粒尺寸。該等研細顆粒隨後凝聚至約150-1000微米,例如約400-700微米。研細的天然的全穀物粉可使用任何業界習知方法凝聚,包括而不限於,使用糖黏結劑溶液。
在本發明再另一態樣中,預膠凝化全穀物粉係研細至約50-420微米,例如50-200微米之顆粒尺寸。該全穀物可使用任何商業可接受的方式來預膠凝化或預處置,包括而不限於,蒸汽處置與煮沸。該等研細的預膠凝化全穀物顆粒隨後凝聚至約150-1000微米,例如400-700微米。
本發明另一態樣包括研細一或多種全穀物粉,其選自於由天然的、預膠凝化及根據本揭示內容製得的水解全穀物粉所構成之群組。該全穀物粉係研細至約50-420微
米,例如50-200微米之顆粒尺寸。該等研細的預膠凝化全穀物顆粒隨後凝聚至約150-1000微米,例如150-700微米,包括400-700微米。
目前還沒有出現藉由縮減顆粒尺寸並隨後凝聚以改善穀物在液體或半固體的可分散性之改善全穀物口感的方法。又,容易搖動或攪拌根據本發明製得的凝聚化全穀物以供食用大量全穀物的能力從市場性與消費者接受度的觀點來看不僅有利,而且業界亦尚未知悉。
根據本發明態樣製得的凝聚化全穀物粉在整個處理過程當中保持全穀物的狀態。因此,“全穀物”健康聲明可由根據本發明製得之粉做到。
根據本發明製備的高度可分散全穀物粉可用於提供消費者可飲用之穀物產品。舉例來說,根據本發明製備的水解燕麥粉可加至水、奶、果汁、優格、布丁等等,以製得營養且容易食用的全穀物燕麥可飲用點心。又,由於水解全穀物粉係高度可分散於液體與半固體,可飲用點心亦很快且容易製備。同樣地,天然的與微膠凝化粉可加至水、奶、果汁、優格、布丁等等,以製得全穀物可飲用點心。
根據本案所述方法製得的高度可分散燕麥粉相較於未處理燕麥或天然的燕麥粉係含有增加的燕麥蒽醯胺位準。尤其,天然的燕麥粉含有約0.0002-0.03%總燕麥蒽醯胺。燕麥蒽醯胺為僅於燕麥中發現的多酚類。燕麥蒽醯胺已被顯示具有顯著抗氧化活性且由於其強力抗氧化活性而
關連至許多有益的健康活性。體內測試已顯示燕麥蒽醯胺的抗氧化能力提供了健康益處,例如減少的LDL氧化比率,於是防止癌症和心臟疾病。燕麥蒽醯胺2c的結構顯示於下:
申請人已發現存在於燕麥中的三種主要燕麥蒽醯胺-2c、2p與2f-的位準由於本案所述方法全都增加了。尤其,藉由上述用於製備可溶性燕麥粉之方法,總燕麥蒽醯胺位準(包括2c、2p與2f)相較於天然的全燕麥粉係提升約20-35%。
實施例1
所得可溶性燕麥粉的燕麥蒽醯胺位準係使用逆相HPLC測量。將簡單去殼穀物萃取、乾燥並重新懸浮成等分試樣。等分試樣係藉由帶有C-18管柱之HPLC,使用二極管陣列分光光度計檢測儀於340nm檢測。該峰係藉由比對真實燕麥蒽醯胺的標準曲線來定量。此測試結果係例示於圖1A與圖1B。亦發現到根據本案所述方法製得之可溶性燕麥粉的燕麥蒽醯胺含量比起僅僅使用擠壓(無酶)處理的燕麥粉係具有較高的燕麥蒽醯胺含量。
尤其,圖3A繪示了在天然的全燕麥粉、擠壓粉與根據本發明製得的SoluOat 100粉樣本中的燕麥蒽醯胺2c、
燕麥蒽醯胺2p、燕麥蒽醯胺2f與總燕麥蒽醯胺(2c+2p+2f)位準。如本案所用,“SoluOat 100”或“SoluOat 100粉”-無論單複數-應指根據本揭示內容列示方法所製得的99.5%全燕麥粉與0.5%混合生育醇。
如圖3A所示,燕麥蒽醯胺2c、2p與2f、及總燕麥蒽醯胺含量的最高位準係於SoluOat 100粉中發現。尤其,天然的全燕麥粉被發現含有約35ppm總燕麥蒽醯胺,而SoluOat 100粉被發現含有超過40ppm總燕麥蒽醯胺,結果SoluOat 100粉中的燕麥蒽醯胺位準相較於天然的全燕麥粉有20%增量。在圖3B中,進行了測試天然的全燕麥粉與根據本發明製得之SoluOat 100粉的燕麥蒽醯胺含量的類似測試。如圖3B所示,天然的全燕麥粉被發現具有約35ppm總燕麥蒽醯胺,而SoluOat 100粉含有約45ppm總燕麥蒽醯胺。於是,相較於天然的全燕麥粉,SoluOat 100粉展現35%增量之總燕麥蒽醯胺位準。
經由本案所述具體例製得的可溶性燕麥纖維之增加的燕麥蒽醯胺含量係出乎意料,因為此抗氧化劑為非澱粉植物營養素。然而,上述的酶方法係用於改善粉的可分散性和溶解性。
亦進行後續分析,以區別各式處理條件所測試之特定燕麥蒽醯胺份量及在處理後發現到的燕麥蒽醯胺位準。下表標識所測試的各種方法條件:
下表標識在不同處理條件之燕麥粉發現到的燕麥蒽醯胺位準連同燕麥蒽醯胺含量的增加。根據本揭示內容擠壓與水解的表中所有樣本為SoluOat 100,其係如上文所定義者。
根據上表還有圖4所顯示的結果,在三個主要燕麥蒽醯胺(2c、2p、2f)當中,燕麥蒽醯胺2c具有最高的體外
抗氧化活性。就體內活性而言,燕麥蒽醯胺2p具有最高的生物利用率。單單擠壓稍微增加了總燕麥蒽醯胺含量(3.72%),但大幅增加了燕麥蒽醯胺2p含量(27.79%)。酶解消化增加了總計與個別燕麥蒽醯胺含量,包括2c、2p、與2f的含量。於固定的酶濃度(0.1%),28%、30%與32%之水份位準使總燕麥蒽醯胺含量相較於全燕麥粉分別增加了6.47%、15.26%、及22.47%。水份含量或水份位準係於混合物進入擠壓機時測量。於32%的固定水份位準,0.12%與0.20%之酶濃度在相較於0.1%之酶濃度時並無增加燕麥蒽醯胺含量。
再者,根據本案方法製得的高度可分散燕麥粉亦證實了壓制NF-κB的能力。NF-κB為免疫反應/發炎觸發劑。尤其,減少之NF-κB在臨床上係關連到慢性發炎減少。抗發炎活性係藉由NF-κB抑制性試驗測量。將人類293T細胞於標準培養基中以胎牛血清與抗生素培養過夜,接著4-小時無血清“挨餓”期。具本領域通常技術者將認知到,“挨餓的”細胞為具有無血清培養基的細胞,以消除胎牛血清的效應且因此該細胞對TNF處理較為敏感。之後,細胞係以TNF-α(100ng/mL)與測試樣本萃取物於37℃與CO2處理一小時。萃取全細胞蛋白質並使用TransAM NF-κB ELISA套組測量NF-κB位準。下表顯示測試結果,將全燕麥粉和SoluOat 90%及空白組比對。本案所用的“SoluOat”、SoluOat粉”、“SoluOat 90”或“正規SoluOat”-無論單複數-應指根據本揭示內容列示方法所製造的90%全燕麥粉5%糖、4.5%麥芽糊精與
0.5%混合生育醇。
圖5例示樣本中的NF-κB抑制百分比。
本發明可以其他特定形式具體化,而無逸離其精神或基本特性。前述具體例-因此-在所有方面都被認為是例示性,而非限制本案所述發明。本發明範疇於是係由隨附請求項-而非由前述說明-所指明,本發明係意圖涵蓋及於請求項等效性之意義與範圍的所有變化。
Claims (13)
- 一種高度可分散全穀物燕麥粉,其相較於天然的全燕麥粉含有更多約20-35%之燕麥蒽醯胺,其中該全穀物燕麥粉係在水解、造粒及研磨之後凝聚。
- 如請求項1之高度可分散全穀物燕麥粉,其中該粉的燕麥蒽醯胺含量係比天然的全穀物燕麥粉高約35%。
- 如請求項1之高度可分散全穀物燕麥粉,其中該燕麥粉展現NF-κB抑制活性,其中該NF-κB抑制活性比天然的全穀物燕麥粉係至少高約25%。
- 一種高度可分散全穀物燕麥粉,其係使用下列方法製造:a.將天然的全穀物燕麥粉起始混合物和水性酶溶液組合,以形成一具有25至40wt%水份含量之酶起始混合物;b.加熱該酶起始混合物;c.將該經加熱的起始混合物添加至一擠壓機並擠壓該混合物,直到混合物的溫度增加至約260℉至300℉,其中該酶被失活;d.將該經擠壓的粉造粒;e.乾燥該經造粒且經擠壓的粉;f.研磨該經造粒且經擠壓的粉至約50-420微米之顆粒尺寸;g.將該經研磨且經擠壓的粉凝聚至約150-1000微 米之顆粒尺寸其中該高度可分散全穀物燕麥粉相較於天然的全燕麥粉係含有至少20%較高位準之燕麥蒽醯胺。
- 如請求項5之高度可分散全穀物燕麥粉,其中該酶為α-澱粉酶。
- 如請求項5之高度可分散全穀物燕麥粉,其中該酶起始混合物包含0.01-0.5wt% α-澱粉酶。
- 如請求項4之高度可分散全穀物燕麥粉,其中該酶起始混合物包含約0.15wt% α-澱粉酶。
- 如請求項4之高度可分散全穀物燕麥粉,其中該起始混合物進一步包含糖及任擇之麥芽糊精。
- 如請求項4之高度可分散全穀物燕麥粉,其中在該擠壓機中的酶起始混合物之水份含量為約28-32%。
- 如請求項4之高度可分散全穀物燕麥粉,其中該粉的燕麥蒽醯胺含量比起天然的全穀物燕麥粉係高約35%。
- 如請求項4之高度可分散全穀物燕麥粉,其中該燕麥粉展現NF-κB抑制活性,其中該NF-κB抑制活性比起天然的全穀物燕麥粉係至少高約25%。
- 如請求項4之高度可分散全穀物燕麥粉,其中在該酶失活之後,該燕麥粉離開該擠壓機。
- 如請求項4之高度可分散全穀物燕麥粉,其中該起始混合物進一步包含混合生育醇。
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-
2013
- 2013-03-15 US US13/833,717 patent/US9011947B2/en active Active
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2014
- 2014-03-07 CA CA2905746A patent/CA2905746C/en active Active
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- 2014-03-07 MX MX2015013033A patent/MX346373B/es active IP Right Grant
- 2014-03-07 WO PCT/US2014/021913 patent/WO2014150029A1/en active Application Filing
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- 2014-03-07 RU RU2015144065A patent/RU2606829C1/ru active
- 2014-03-07 BR BR112015022808A patent/BR112015022808A8/pt not_active Application Discontinuation
- 2014-03-07 EP EP14767672.0A patent/EP2968432A4/en not_active Ceased
- 2014-03-14 TW TW103109637A patent/TW201438593A/zh unknown
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CA2905746A1 (en) | 2014-09-25 |
AU2014237555A1 (en) | 2015-11-05 |
CN105228639A (zh) | 2016-01-06 |
BR112015022808A2 (pt) | 2017-07-18 |
WO2014150029A1 (en) | 2014-09-25 |
EP2968432A4 (en) | 2016-07-27 |
US20130209610A1 (en) | 2013-08-15 |
AU2014237555C1 (en) | 2017-06-22 |
MX346373B (es) | 2017-03-16 |
CA2905746C (en) | 2016-11-08 |
US9011947B2 (en) | 2015-04-21 |
EP2968432A1 (en) | 2016-01-20 |
MX2015013033A (es) | 2016-05-18 |
CN105228639B (zh) | 2019-04-02 |
BR112015022808A8 (pt) | 2019-11-26 |
AU2014237555B2 (en) | 2016-06-09 |
RU2606829C1 (ru) | 2017-01-10 |
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