CN1309719A - 由酚氧化酶改性多糖 - Google Patents
由酚氧化酶改性多糖 Download PDFInfo
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- CN1309719A CN1309719A CN98812431A CN98812431A CN1309719A CN 1309719 A CN1309719 A CN 1309719A CN 98812431 A CN98812431 A CN 98812431A CN 98812431 A CN98812431 A CN 98812431A CN 1309719 A CN1309719 A CN 1309719A
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- polysaccharide
- alkyl
- oligosaccharides
- salt
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Abstract
本发明涉及将寡糖或多糖的糖单体的C1和/或C2和/或C3和/或C4和/或C5和/或C6的羟基氧化的方法,包括在含水介质中让寡糖或多糖与酚氧化酶和增强剂接触,据此产生与天然寡糖或多糖相比已改变特性的寡糖或多糖。
Description
发明领域
本发明涉及水溶性以及水不溶性寡糖或多糖如淀粉和纤维素的酶促氧化方法,其中寡糖或多糖被氧化后引入羰基和/或羧基而得到了功能性质改善的产物。
背景技术
由各种化学方法氧化多糖的方法是现有技术中已知的:
纤维素的氧化,例如,会引起所得到分子的结构和结晶度的变化,进而影响其化学和物理性能。Varma和Chavan[Varma,A.J.,和Chavan,V.B.(1995),聚合物降解和稳定性,49,第245-250]发现了在结晶度的减少和氧化程度的提高之间的比例性。此外,通过由高碘酸盐氧化法将纤维素氧化成2,3-二醛纤维素和随后由亚氯酸钠将2,3-二醛纤维素氧化成2,3-二羧基纤维素,Varma和Chavan从纤维素生产出了2,3-二羧基纤维素钠。98%的2,3-二羧基纤维素钠发现是水溶性的。
此外,氧化的多葡糖苷具有有益的性能,它可作为钙的多价螯合剂,并可在洗涤剂配方中用作三聚磷酸盐的替代品[Santacesaria,E.,Trulli,F.,Brussani,G.F.,Gelosa,D.,和Di Serio,M.(1994),碳水化合物聚合物,23,第35-461]。
此外,各种类型的多糖,尤其淀粉,除了在印花和织物整理中用作加工助剂外,还在纺织工业中作为浆料有着极重要的意义。然而,天然淀粉的性能与特殊应用所要求的性能相比并不总是最佳的。天然淀粉的诸多问题中的一个是分子尺寸非常大,不溶,粘稠溶液在不同温度下的不稳定性,且其容易遭受微生物降解作用。因此,淀粉的化学改性已成为克服这些问题和生产出与天然淀粉相比已改变特性的淀粉的重要手段。通常的处理包括酸处理,氧化,醚化,酯化,接枝,和制备聚(乙烯基)-淀粉复合物[Abdel-Hafiz,S.A.(1997),聚合物降解和稳定性,55,第9-16页]。
还有,Hebeish等人[Hebeish,A.,El-Kashouti,M.A.,Abdel-Thalouth,I.,Haggag,K.,和El-Halwagi,A.(1994),《纤维素化学与技术》,28,第409-418页]描述道,生产羧甲基纤维素(CMC)时的取代度取决于纤维素基础物质的氧化程度,因此通过使用氧化程度不同的纤维素能够生产出各种质量的CMC。
因此越来越关注和需要一些能够在寡糖和多糖中引进各种类型的氧化变化的方法。
发明概述
本发明涉及将寡糖或多糖的糖单体的C1和/或C2和/或C3和/或C4和/或C5和/或C6的羟基氧化的方法,包括在含水介质中让寡糖或多糖与酚氧化酶,以及过氧化氢源(当酚氧化酶是过氧化物酶时)和增强剂一起接触,据此产生与天然寡糖或多糖相比已改变特性的寡糖或多糖。
附图的简述
本发明进一步参照附图来说明,其中:
图1说明了棉纤维素的渐进氧化的理想模式。
图2显示了未处理的白色棉以及用Tempo/漆酶处理的白色棉的覆盖范围1800-1500cm-1的FT-IR/PAS谱,如实施例1中所述。
本发明的详细叙述
本发明的目的是对寡糖或多糖进行酶促氧化改性,据此产生新的官能团。
因此,我们已经创造出将寡糖或多糖的糖单体的C1和/或C2和/或C3和/或C4和/或C5和/或C6的羟基加以氧化的方法,包括在含水介质中让寡糖或多糖与酚氧化酶,以及过氧化氢源(当酚氧化酶是过氧化物酶时)和增强剂一起接触,据此产生与天然寡糖或多糖相比已改变特性的寡糖或多糖。
尤其我们已经创造出将寡糖或多糖的糖单体的C2和/或C3和/或C6的羟基氧化的方法,包括在含水介质中让寡糖或多糖与酚氧化酶,以及过氧化氢源(当酚氧化酶是过氧化物酶时)和增强剂一起接触,据此产生与天然寡糖或多糖相比已改变特性的寡糖或多糖。
特别是,我们已经创造出将寡糖或多糖的糖单体的C6的羟基氧化的方法,包括在含水介质中让寡糖或多糖与酚氧化酶,以及过氧化氢源(当酚氧化酶是过氧化物酶时)和增强剂一起接触,据此产生与天然寡糖或多糖相比已改变特性的寡糖或多糖。
根据本发明,低多糖含有至少20个单体,优选至少50个单体,尤其至少100个单体。
根据本发明的氧化会导致在寡糖或多糖中产生羰基(酮和醛)和/或羧基,得到与天然寡糖或多糖相比特性改变的寡糖或多糖。
在图1中说明了棉纤维素的渐进氧化的理想化模式的一个例子。此模式说明了用渐进氧化所能预期到的棉纤维素的一些类型的变化。所形成的羰基或羧基的数目将随氧化程度的提高而增加:“A”说明未改性的葡萄糖;“B”说明在C6形成羰基;“C”说明在C2,C3,和C6形成羰基;“D”说明在C2和在C3形成羰基,在C6形成羧基;“E”说明在C2形成羰基,在C3和C6形成羧基;开环;“F”说明聚合物断裂和可能的物质损失;和“G”说明了新物质的出现和氧化。
正常情况,有益的氧化是在C6特异性氧化(在其它碳原子上没有或仅仅有限的氧化)成羰基或羧基;在本发明中描述的酶促氧化尤其适合该特异和“精细”的氧化。
与天然寡糖或多糖相比的区别是氧化本身的结果,但所希望的差别常常通过由其它方式如化学和/或酶促改性方法对寡糖或多糖中所引进的那些变化进一步改性来实现。
例如,表面电荷改变、和/或可染性改变、和/或染色特异性改变、和/或具有新的官能团使得有可能共价或非共价连接和/或吸附本身含有或携带其它有用官能团的化合物、使聚合物链有可能交联的新型寡糖或多糖(例如从纤维素衍生而来),或天然寡糖或多糖和人工合成聚合物的复合物/掺混物,在制备后用于纺织品制造中,可以生产出无皱织物、耐久压烫的织物、强度提高的织物、防水性织物、阻燃性织物、持久柔软性提高的织物、防污织物和/或获得抗静电外观。检查多糖氧化的方法
指示棉氧化程度的两个因素是官能团如羰基和羧基的形成,和由于聚合物分裂或断链导致的织物强度的损失。因此,氧化的分析能够通过测量织物撕裂强度或通过测量所引入的官能团来进行。
织物撕裂强度试验,通常涉及测量促使织物中撕裂扩大所需要的力,能够用于提供织物损坏的量度指示。然而,需要有几个重复试验来获得合理的结果,且由于纤维缺陷使得在各重复试验之间有较大的变化[Cardamone,J.M.,和Brown,P.(1986),Historic Textile and Paper,第3章,ACS,华盛顿]。当考虑比较类似的样品时,在各再现试验之间的变化可能会超过样品之间的变化,这使比较更为困难。也必须考虑的是,在加工过程中对织物的机械损伤将导致总体织物强度的损失,因此撕裂强度的测量值反映的不只是氧化损坏作用。
纤维素的氧化最初导致形成羰基,进一步氧化导致形成羧酸或羧基阴离子(这取决于pH)。
用于测定羧基和羰基的染色法已经广泛用于指示棉织物中氧化的程度。Tollen氏试剂(Ag(NH3)2OH)在氧化的棉中的使用将由于银金属的沉淀而导致全部醛基的黑色染色[Skoog,D.A.,West,D.M.,和Holler,F.J.(1992),分析化学的基本原理(Fundamentalsof AnalyticalChemistry),第20章,Saunders College Publishers,Fl]。其它着色剂如2,4-二硝基苯肼能够用于识别酮和醛。相对的酮量因此可通过扣除来测定。亚甲基蓝溶液能用于通过染色鉴定棉织物上的羧基,这是由于亚甲基蓝阳离子吸附在纤维素羧基上导致的[Lewin,M.,和Sello,S.B.(Ed.)(1984),纤维和织物的化学处理:基本原理和制备,部分B,Marcel Dekker Inc.NY]。尽管染色法可用于指示氧化的区域,但是,没有广阔的标准品系列的制备,它们就不能达到氧化的定量测量,并且染色法不能显示特异性氧化。这些染色法相当费时和乏味,而且很难用于早已着色的染色织物。
所形成的羰基和羧基的测量也能够通过使用振动光谱技术如傅里叶变换红外光谱法(FTIR),漫反射FTIR(DRIFT),和FTIP/光声谱法(FTIR/PAS)来实现。
棉纤维素上绝大多数羰基的红外吸收谱带可在光谱的1700-1750cm-1区域中观察到,而棉纤维素的羧基谱带通常可在1550-1600cm-1区域中观察到,因此有利于由IR分析法测量氧化[Cardamone,J.M,Gould,J.M.,和Gordon,S.H.(1987),纺织品研究杂志(Text.Res.J.),57(4),第235-239页,Yang,C.Q.,和Fateley,W.G.(1990),应用光谱学(Appl.Spectrosc.),44,第1035-1041页,Yang,C.Q.(1991),应用光谱学,45(1),第102-108页]。
Cardamone和Brown[Cardamone,J.M.,和Brown,P.(1986),HistoricTextile and Paper,Ch.3.,ACS,Washington]通过测量FTIR/PAS谱的1540-1850cm-1区域的积分面积来对比人工和自然老化的棉,说明了最好地再现自然老化过程的条件。Yang和他的各位合作者[Yang,C.Q.,和Fateley,W.G.(1990),应用光谱学,44,第1035-1041页,Yang,C.Q.(1991),应用光谱学,45(1),第102-108页],也对棉氧化的测量进行了研究,他们使用的是诸如DRIFTS,FTIR-PAS和衰减全反射(Attenuated Total Reflectance)之类的技术。对来自研磨棉样品的疏松材料的对比,和由Yang和Fateley通过使用FTIR/PAS进行的表面测量[Yang,C.Q.,和Fateley,W.G.(1990),应用光谱学,44,第1035-1041页],说明了棉织物的氧化通常是一个表面特征,当研究疏松样品时,氧化的迹象即使没有完全消除,也是会大大减少了。
羰基和羧基的相对量能够用作纤维素氧化的指示并能够通过使用振动光谱学来测量。使用振动光谱技术如DRIFTS和PAS对棉织物的近表面分析已经成功地用来测量由于老化和加工处理导致的纤维素氧化[Cardamone,J.M,Gould,J.M.,和Gordon,S.H.1987),纺织品研究杂志,57(4),第235-239页,Kokot,S.,和Jermini,M.,(1994),纺织品研究杂志,64(2),第100-105页,Yang,C.Q.,和Fateley,W.G.(1990),应用光谱学,44,第1035-1041页]。
Kokot和各位合作者[Kokot,S.,和Jermini,M.,(1994),纺织品研究杂志,64(2),第100-105页,Kokot,S.,Marahusin,L.,Schweinsberg,D.P.,和Jermini,M.(1994),纺织品研究杂志,4(12),第710-716页]也采用振动光谱学(DRIFTS形式)来测量棉的氧化。在此研究中,通过使用化学计量方法如主成分分析(Principal ComponentAnalysis)和偏最小二乘方回归法(Partial Least Squares Regression)来分析一系列经历过模拟漂白过程的织物的光谱。利用波数范围1750cm-1-1700cm-1和1575cm-1-1550cm-1。(它们与羰基和羧基的形成相符),Kokot等人将氧化到不同程度的棉纱相互分离开以及与天然棉纱分离开。这一工作重点强调了经受不同水平的氧化的棉的鉴别中羰基和羧基光谱区域的重要性以及在光谱数据的分析中使用多变量分析(化学计量法)的必要性。
由Yang和Fateley对风化与未风化织物的对比[Yang,C.Q.,和Fateley,W.G.(1990),Appl.Spectrosc.,44,第1035-1041页]重点显示出风化织物的吸收谱带在1722和1704cm-1范围。这些谱带属于羰基吸收。Cardamone等人(Cardamone,J.M,Gould,J.M.,和Gordon,S.H.(1987),纺织品研究杂志,57(4),第235-239页]研究了自然和人工老化的棉纺织品,以对比在不同环境中发生的氧化损害的程度。由PA光谱的1540-1850cm-1范围的积分面积获得了氧化程度的度量。这一研究说明了测量所选择光谱区域可指示纤维素氧化。
Kokot和Jermini[Kokot,S.,和Jermini,M.,(1994),纺织品研究杂志,64(2),第100-105页]使用DRIFTS来表征棉织物,它已经由电产生的氧处理导致氧化损坏。化学计量技术在这一工作中的应用重点显示了在经受不同水平的氧化损坏的棉的鉴定中羰基和羧基光谱区域的重要性。多糖
各种类型的天然碳水化合物型聚合物(寡糖和多糖)以及基于各种类型碳水化合物单体的人工制造的(人造的)聚合物,以及化学衍生的/改性的天然或人造多糖以及含有碳水化合物单元的共聚物能够由酚氧化酶与合适的增强剂相结合进行氧化改性。
基于这一发现,现已有可能由酶促方法对寡糖或多糖,含有可溶性或不溶性聚合物纤维(尤其纤维素纤维)的织物、纱等进行化学改性,在该方法中酚氧化酶如过氧化物酶或漆酶,与增强剂相结合,催化在寡糖或多糖中引入新的官能团如羰基和/或羧基。
因此,本发明提供了对含有游离羟基的可溶性或不溶性寡糖或多糖进行酶促氧化使之含羰基或羧基的方法,在该方法中可溶性或不溶性寡糖或多糖与酚氧化酶以及能够催化氧化反应的增强剂一起进行反应。
根据本发明的酶促氧化是正常的“温和”氧化,得到有较多数目的羰基和/或羧基的寡糖或多糖,但没有或很少有开环。对于大多数目的来说,开环和/或聚合物断裂均是不希望的。
这一酶促改性的寡糖或多糖是进一步改性用的很好的起始原料,因为羰基和羧基比羟基更具反应活性。因此能够制造出具有改进性能的纺织品、纤维、纱等。这些性能的例子是耐压烫性,软化,防污,拒水性和阻燃性。本发明提供一种方法,由该方法,取决于条件的选择(酶,增强剂,温度,PH值等),能够以容易、经济和环保的方式获得或改进一种或多种所希望的性能。寡糖和多糖的所希望的性能通常可在根据本发明酶促氧化之后由其它措施如化学和/或酶促改性方法进一步改性来获得。
在本说明书和权利要求中,术语“寡糖或多糖”是指基于那些具有可氧化成羰基和/或羧基的羟基的糖单体的聚合物质。
尤其有趣的是基于下面糖(单体)的寡糖或多糖,它们或者是均聚物(基于一种单体的聚合物),或者是杂聚物(基于两种或更多种不同单体的聚合物):
丁醛糖和丁酮糖如赤藓糖和赤藓酮糖;戊醛糖如阿拉伯糖,核糖,和木糖;戊酮糖如核酮糖和木酮糖;己醛糖如葡萄糖、半乳糖和甘露糖;己酮糖如果糖和山梨糖;和糖衍生物包括脱氧糖如脱氧核糖、鼠李糖和岩藻糖,氨基糖如葡糖胺,酸性的碳水化合物如葡糖醛酸、半乳糖醛酸、甘露糖醛酸和古洛糖醛酸(guluronic acid)。
更优选的是天然碳水化合物聚合物(寡糖和多糖)和它们的水解产物,如纤维素,半纤维素,淀粉,木聚糖,黄原胶,瓜耳胶,阿拉伯树胶,刺梧桐树胶,gellan胶,豆角胶,魔芋胶(konjak),凝胶多糖,kappa角叉菜胶,藻酸盐,琼脂,果胶(高甲氧基,低甲氧基和酰胺化果胶和它们的混合物),果胶酸盐,粘胶,羟丙基纤维素,壳多糖,裂褶多糖(schizophylan),脱乙酰壳多糖,肝素,葡聚糖,菊粉,果聚糖。
优选地,进行本发明的方法处理的多糖材料是以纤维,人造短纤维如溶纺纤维,长丝,线,纱,或纺织品织物(机织,非机织或针织)形式存在。
在本发明的优选实施方案中,多糖是纤维素聚合物纤维,即含有纤维素或纤维素衍生物(优选从棉制得),粘胶(人造纤维),lyocell,亚麻,苎麻,或它们的任何混纺物;和它们与聚酯,羊毛,聚酰胺和(聚)丙烯酸类的混纺物。混纺物的典型实例是粘胶/棉,粘胶/聚酯,lyocell/聚酯,lyocell/棉,棉/聚丙烯酸类,棉/聚酯,棉/聚酯/丙烯酸类,棉/聚酰胺/聚酯。
在本发明的另一个优选实施方案,多糖是基于糖单体或化学衍生的糖单体的合成多糖,以及糖单体的共聚物或多糖和其它聚合物单体或聚合物材料。酚氧化酶
合适的酚氧化酶的例子,即对芳族化合物、尤其是酚和/或多酚化合物起作用的酶,是过氧化物酶(EC1.11.1.7),漆酶(EC1.10.3.2),胆红素氧化酶(EC1.3.3.5),单酚单加氧酶(monophenol monooxygenases)(EC1.14.18.1)和儿茶酚氧化酶(EC1.10.3.1)。过氧化物酶
根据本发明,合适的过氧化物酶可以是属于酶分类(EC1.11.1.7)的任何过氧化物酶,或从它衍生的显示有过氧化物酶活性的任何片段。
优选地,在本发明方法使用的过氧化物酶是由植物(例如辣根或大豆过氧化物酶)或微生物如真菌或细菌产生的。一些优选的真菌包括属于半知菌亚门(Deuteromycotina)丝孢纲(Hyphomycetes),例如镰孢属(Fusarium)、腐质霉属(Humicola)、Tricoderma属,漆斑菌属(Myrothecium),轮枝孢属(Verticillum)、节线菌属(Arthromyces)、卡尔黑霉属(Caldariomyces)、Ulocladium属、Embellisia属、枝孢属(Cladosporium)或Dreschlera属的菌株,尤其是尖镰孢(Fusariumoxysporum)(DSM2672)、Humicola insolens、Trichoderma resii、疣孢漆斑菌(Myrothecium verrucana)(IFO6113)、黄萎轮枝孢(Verticillum alboatrum)、大丽花轮枝孢(Verticillum dahlie)、Arthromyces ramosus(FERM P-7754)、烟曲卡尔黑霉(Caldariomycesfumago)、Ulocladium chartarum、Embellisia alli或Dreschlerahalodes。
其它优选的真菌包括属于担子菌亚门(Basidiomycotina)担子菌纲(Basidiomycetes),例如鬼伞属(Coprinus)、Phanerochaete、革盖菌属(Coriolus)或栓菌属(Trametes)的菌株,尤其是Coprinus cinereus f.Microsporus(IFO 8371)、长根鬼伞(Coprinus macrorhizus)、Phanerochaete chrysosporium(例如NA-12)或栓菌如变色栓菌(T.versicolor)(例如PR4 28-A)。
进一步优选的真菌包括属于接合菌亚门(Zygomycotina)Mycoraceae纲的菌株,例如根霉(Phizopus)或毛霉(Mucor),尤其是冻土毛霉(Mucor hiemalis)。
一些优选的细菌包括属于放线菌目(Actinomycetales)的菌株,例如类球形链球菌(Streptomyces spheroides)(ATTC 23965)、热紫链霉菌(Streptomyces thermoviolaceus)(IFO 12382)或轮丝链轮丝菌轮丝亚种(Streptoverticillum verticillium ssp.verticillium)。
其它优选的细菌包括短小芽孢杆菌(Bacillus pumilus)(ATCC12905),嗜热脂肪芽孢杆菌(Bacillus stearothermophilus),类球红细菌(Rhodobacter sphaeroides),沼泽单孢紫红菌(Rhodomonaspalustri),乳酸链球菌(Streptococcus lactis),Pseudomonaspurrocinia(ATCC 15958)或荧光假单胞菌(Pseudomonas fluorescens)(NRRL B-11)。
进一步优选的细菌包括属于粘球菌属(Myxococcus)的菌株,例如,变绿粘球菌(M. virescens)。
尤其优选重组生产的过氧化物酶,例如,衍生自WO 92/16634的鬼伞,尤其是长根鬼伞或灰盖鬼伞的过氧化物酶,或它们的变体,例如WO94/12621中描述的变体。漆酶
合适的漆酶已知来自微生物和植物。微生物漆酶可从细菌或真菌(包括丝状真菌和酵母菌)获得。合适的例子包括从曲霉属(Aspergillus)、脉孢菌属(Neurospora)例如粗糙脉孢菌(N.crassa)、柄孢壳属(Podospora)、葡萄孢属(Botrytis)、金钱菌属(Collybia),层孔菌属(Fomes),香菇属(Lentinus),侧耳属(Pleurotus),栓菌属例如绒毛栓菌(T.villosa)和变色栓菌(T.versicolor)、丝核菌属(Rhizoctonia)例如立枯丝核菌(R.solani)、鬼伞属例如褶纹鬼伞(C.plicatilis)和灰盖鬼伞、小脆柄菇属(Psatyrella)、毁丝霉属(Myceliophthora)例如嗜热毁丝霉(M.thermophila)、小柱孢菌属(Scytalidium)、多孔菌属(Polyporus)例如P.pinsitus、射脉菌属(Phlebia)例如射脉菌(P.radita)(WO 92/01046),或革盖菌属(Coriolus)例如毛革盖菌(C.hirsutus)(JP2-238885)的菌株获得的漆酶,尤其是得自栓菌属、毁丝霉属、小柱孢菌属或多孔菌属的漆酶。酚氧化酶体系
如果该酚氧化酶需要过氧化氢源,该源可以是过氧化氢或可就地产生过氧化氢的过氧化氢前体,例如过碳酸盐或过硼酸盐,或产生过氧化氢的酶体系,例如氧化酶和该氧化酶的底物,或氨基酸氧化酶和合适的氨基酸,或过羧酸或其盐。过氧化氢可在该过程中的开始或期间,以例如相当于0.001-25mM H2O2的浓度添加。
如果该酚氧化酶需要分子氧,来自大气的分子氧通常以足够的量存在。增强剂
一般而言,属于酚氧化酶的底物的任何化合物都可用作增强剂。除杂环化合物外,还包括具有官能团如-OH,-NH,和-SH的芳族化合物。
其中式X表示(-O-)或(-S-),取代基R1-R9可相同或不同,它们独立地表示下面基团中的任何一种:氢,卤素,羟基,甲酰基,羧基和它的酯和盐,氨基甲酰基,磺基和它的酯和盐,氨磺酰基,硝基,氨基,苯基,C1-C14-烷基,C3-C5-烷氧基,羰基-C1-C5-烷基,芳基-C1-C5-烷基;该氨基甲酰基、氨磺酰基和氨基可进一步是未取代的或被取代基R10取代一次或两次;该苯基进一步是未取代的或被一个或多个取代基R10所取代;这些C1-C14-烷基,C1-C5-烷氧基,羰基-C1-C5-烷基,和芳基C1-C5-烷基可以是饱和的或不饱和的,分支的或不分支的,并且进一步是未取代的或被一个或多个取代基R10取代;
该取代基R10表示下面基团中的任何一种:卤素,羟基,甲酰基,羧基和它的酯和盐,氨基甲酰基,磺基和它的酯和盐,氨磺酰基,硝基,氨基,苯基,氨基烷基,哌啶子基,哌嗪基,吡咯烷子基(pyrrolidino),C1-C5-烷基,C1-C5-烷氧基;该氨基甲酰基、氨磺酰基和氨基可进一步是未取代的或被羟基、C1-C5烷基,C1-C5烷氧基取代一次或两次;该苯基可进一步是被一个或多个以下基团所取代:卤素,羟基,氨基,甲酰基,羧基和它的酯和盐,氨基甲酰基,磺基和它的酯和盐,和氨磺酰基;该C1-C5烷基和C1-C5烷氧基可进一步是饱和的或不饱和的,分支的或不分支的,并且可以进一步被以下基团中的任何基团取代一次或两次:卤素,羟基,氨基,甲酰基,羧基和它的酯和盐,氨基甲酰基,磺基和它的酯和盐,和氨磺酰基;
或在该通式中,取代基R1-R9中的两个可一起形成基团-B-,其中B表示下列基团中的任何一种:(-CHR10-N=N-),(-CH=CH-)n,(-CH=N-)n,或(-N=CR10-NR11-),其中n表示1-3中的整数,R10是以上所定义的取代基,R11与R10定义相同。
在更具体的实施方案中,增强剂是10-甲基吩噻嗪,吩噻嗪-10-丙酸,吩噻嗪-10-丙酸N-羟基琥珀酰亚胺酯,10-乙基-吩噻嗪-4-羧酸,10-乙基吩噻嗪,10-丙基吩噻嗪,10-异丙基吩噻嗪,吩噻嗪-10-丙酸甲酯,10-苯基吩噻嗪,10-烯丙基吩噻嗪,10-(3-(4-甲基哌嗪-1-基)丙基)吩噻嗪,10-(2-吡咯烷-1-基-乙基)吩噻嗪,2-甲氧基-10-甲基吩噻嗪,1-甲氧基-10-甲基吩噻嗪,3-甲氧基-10-甲基吩噻嗪,3,10-二甲基吩噻嗪,3,7,10-三甲基吩噻嗪,10-(2-羟乙基)吩噻嗪,10-(3-羟丙基)吩噻嗪,3-(2-羟乙基)-10-甲基吩噻嗪,3-羟甲基-10-甲基吩噻嗪,3,7-二溴吩噻嗪-10-丙酸,吩噻嗪-10-丙酰胺,氯丙嗪,2-氯-10-甲基吩噻嗪,2-乙酰基-10-甲基吩噻嗪,10-甲基吩噁嗪,10-乙基吩噁嗪,吩噁嗪-10-丙酸,10-(2-羟乙基)吩噁嗪或4-羧基吩噁嗪-10-丙酸。
增强剂也可由下式Ⅱ表述:在该式中A是基团如-D,-CH=CH-D,-CH=CH-CH=CH-D,-CH=N-D,-N=N-D,或-N=CH-D,其中D选自-CO-E,-SO2-E,-N-XY,和-N+-XYZ,其中E是-H,-OH,-R,或-OR,X和Y和Z可相同或不同并选自-H和-R;R是C1-C16烷基,优选C1-C8烷基,该烷基是饱和的或不饱和的,分支的或不分支的,并可任意性地被羧基、磺基或氨基取代;B和C可相同或不同,并选自CmH2m+1;1fmf5.
在优选的实施方案中,在以上通式中的A是-CO-E,其中E可以是-H,-OH,-R,或-OR;R是C1-C16烷基,优选C1-C8烷基,该烷基可以是饱和的或不饱和的,分支的或不分支的,并可任意地被羧基、磺基或氨基取代;B和C可相同或不同,并可选自CmH2m+1;1fmf5.
在以上通式中,A也可以位于羟基的间位而不是所显示的对位。
在更具体的实施方案中,增强剂是乙酰基丁香酮(acetosyringone),丁香酸甲酯,丁香酸乙酯,丁香酸丙酯,丁香酸丁酯,丁香酸己酯,或丁香酸辛酯。
增强剂也可以是WO 91/05839中描述的增强剂中的一种,如PHBS,PHBA,香草醛,香豆酸,或肉桂酸。
增强剂也可以是WO 96/18770描述的化合物中的一种,如N-羟基化合物,尤其是含有NO-,N(OH)-,或N(OH)(R1)的脂族、环脂族、杂环或芳族化合物,尤其是N-羟基苯并三唑(HOBT),紫尿酸,或N-羟基乙酰苯胺(HAA)。
其中R1,R2,R3,R4独立地选自氢,卤素,羟基,甲酰基,羧基和它的盐和酯,氨基,硝基,C1-C12烷基,C1-C6烷氧基,羰基(C1-C12烷基),芳基,尤其是苯基,磺基,氨基磺酰基,氨基甲酰基,膦酰基,膦酰氧基,和它们的盐和酯,其中R1,R2,R3,R4可被R5取代,其中R5表示氢,卤素,羟基,甲酰基,羧基和它的盐和酯,氨基,硝基,C1-C12烷基,C1-C6烷氧基,羰基(C1-C12烷基),芳基,尤其是苯基,磺基,氨基磺酰基,氨基甲酰基,膦酰基,膦酰氧基,和它的盐和酯,[X]表示基团(-N=N-),(-N=CR6-)m,(-CR5=N-)m,(-CR7=CR8-)m,和m是1或2。
在本发明的更优选实施方案中,媒介剂是通式Ⅳ的化合物:其中R1,R2,R3,R4独立地选自氢,卤素,羟基,甲酰基,羧基和它的盐和酯,氨基,硝基,C1-C12烷基,C1-C6烷氧基,羰基(C1-C12烷基),芳基,尤其是苯基,磺基,氨基磺酰基,氨基甲酰基,膦酰基,膦酰氧基,和它们的盐和酯,其中R1,R2,R3,R4可被R5取代,其中R5表示氢,卤素,羟基,甲酰基,羧基和它的盐和酯,氨基,硝基,C1-C12烷基,C1-C6烷氧基,羰基(C1-C12烷基),芳基,尤其是苯基,磺基,氨基磺酰基,氨基甲酰基,膦酰基,膦酰氧基,和它的盐和酯,
媒介剂也可以是通式Ⅲ或Ⅳ的盐或酯。
进一步优选的媒介剂是杂环化合物的氧代衍生物和N-羟基衍生物以及杂环化合物的氧代-和甲酰基-衍生物的肟,该杂环化合物包括五元的含氮杂环,尤其是吡咯、吡唑和咪唑以及它们的氢化对应物(例如吡咯烷)及三唑,如1,2,4-三唑;六员的含氮杂环,尤其是一、二和三氮杂己烷类(如哌啶和哌嗪),吗啉和它们的不饱和的对应物(例如吡啶和嘧啶);含有以上杂环作为基本结构的缩合杂环,例如吲哚,苯并噻唑,喹啉和苯并氮杂革。
选自这类化合物的优选媒介剂的实例是吡啶醛肟;N-羟基吡咯烷二酮类如N-羟基琥珀酰亚胺和N-羟基苯邻二甲酰亚胺;3,4-二氢-3-羟基苯并[1,2,3]三嗪-4-酮;甲醛肟三聚物(N,N′,N″-三羟基-1,3,5-三氮杂己烷);和紫尿酸(1,3-二氮杂己烷-2,4,5,6-四酮-5-肟)。
在本发明中还可以使用的媒介剂包括芳族化合物的氧代-和甲酰基-衍生物的肟,如对苯醌二肟和水杨醛肟(2-羟基苯甲醛肟),和N-羟基酰胺类和N-羟基酰基苯胺,如N-羟基乙酰苯胺。
优选的媒介剂选自1-羟基苯并三唑;1-羟基苯并三唑水合物;1-羟基苯并三唑钠盐;1-羟基苯并三唑钾盐;1-羟基苯并三唑锂盐;1-羟基苯并三唑铵盐;1-羟基苯并三唑钙盐;1-羟基苯并三唑镁盐;和1-羟基苯并三唑-6-磺酸。
尤其优选的媒介剂是1-羟基苯并三唑。
以上N-羟基化合物的全部说明应该理解为在相关时包括互变异构体形式如N-氧化物。
尤其,本发明的增强剂可以是在WO 96/18770中公开的任何化合物的对应N-氧基游离基如TEMPO(2,2,6,6-四甲基哌啶子基氧基)。
工业应用
该寡糖或多糖可在含水介质中处理,虽然其它媒介剂/溶剂也能以各种浓度添加,例如,洗涤剂,表面活性剂,润滑剂,有机溶剂,硅油,矿物油,和/或植物油。通常使用在1∶1-20∶1范围内的液体:寡糖或多糖比率,并且通常该处理是在10℃-150℃范围内,优选在40℃-80℃范围内的温度下进行。该处理过程通常进行5-120分钟。典型的酶剂量是0.01-100μg酶蛋白质/g寡糖或多糖,如果添加增强剂,其典型剂量是在0.01-100μmol/g寡糖或多糖范围内。
氧化处理的评价:
如前面所提及的,根据本发明的酶处理可借助于振动光谱技术如FTIR,DRIFT或FTIR-PAS来评价,虽然也可以使用其它光谱技术以及其它技术。通过该技术有可能评价出所获得的氧化程度,以及在寡糖/多糖中引入的氧化变化的分子性质。优选的是,该光谱技术可与多变量分析(化学计量学)相结合以进行详细数据分析,如前面的部分中所述,优选对波数范围1800cm-1-800cm-1、尤其是波数范围1800cm-1-1500cm-1集中进行数据分析,因为这一范围反映了典型的所形成产物。
本发明进一步在下列实施例中进行说明,它们不以任何方式限制本发明的权利范围。
实施例1
棉纤维素:
未染色和未漂白的100%棉斜纹布,195g/m2(从Grenaa DampvaveriA/S,Oesterbrogade 45,DK-8500 Grenaa获得)。根据制造商的指示,在使用之前将该织物用Aquazym Ultra 1200(从Novo Nordisk A/S获得)退浆。退浆之后,该织物被转笼烘燥。将该织物裁切成每块约6g(各大约12×24厘米)的小片。酶:
绒毛栓菌漆酶(TvL)(以前称作Polyporus pinsitus漆酶)(从NovoNordisk A/S获得)。媒介剂:
TEMPO(2,2,6,6-四甲基-1-哌啶基氧基自由基)(Fluka cat# 87903)。处理:
向1200ml总体积不锈钢LOM烧杯中添加:4×6g织物,240ml缓冲剂(0.75g/L KH2PO4调节至pH6),4.7mgTvL,0.015g TEMPO。该LOM烧杯被紧密地封盖并放入耐洗牢度试验仪(Atlas LP2 Launder-O-meter)中,在60℃下处理30分钟。在该处理之后,织物在脱矿质水中漂洗3次并加以干燥。由振动光谱学技术评价:样品制备和光谱各方面:
从织物的各样品上裁切下圆形试片(大约6毫米直径),并在任何实验工作之前将它们在微处理器温度控制器(Clayson IM 1000R培养器)中预先调理至一定湿度(65R.H.)和温度22℃保持1周。
对于FT-IR/PAS实验,将单片的圆形试片放入样品杯(6毫米)中,然后放入到光声测试附件(MTEC Model 200)中。
利用Perkin-Elmer 2000FT-IR光谱仪进行该红外研究。炭黑用作参比材料,在收集光谱数据之前,样品池用氦气吹扫10分钟。在整个范围(4000-450cm-1)内收集光谱测试数据。使用8cm-1的光谱分辨率,128次扫描和0.2cm/s的镜面速度(mirror velocity)。在正常实验室条件(22℃)下收集数据。
未处理的白色棉以及用Tempo/TvL处理的白色棉的覆盖范围1800-1500cm-1的FT-IR/PAS谱显示在图1中。
从图1清楚地看出,Tempo/TvL处理(在图1中表示为“TEMPO”)使羰基含量提高了,因为在1714cm-1、尤其是1734cm-1处的峰强度有提高[Yang,C.Q.(1991),应用光谱学,45(1),第102-108页]。
Claims (16)
1.将寡糖或多糖的糖单体的C1和/或C2和/或C3和/或C4和/或C5和/或C6的羟基加以氧化的方法,包括在含水介质中让寡糖或多糖与酚氧化酶,当酚氧化酶是过氧化物酶时还和过氧化氢源一起,以及增强剂接触,据此产生与天然寡糖或多糖相比已改变特性的寡糖或多糖。
2.根据权利要求1的方法,其中该方法是C6的羟基的氧化。
3.根据权利要求1的方法,其中该含水介质另外包括下式Ⅰ的增强剂:
在式中,X表示(-O-)或(-S-),取代基R1-R9可相同或不同,它们独立地表示下面基团中的任何一种:氢,卤素,羟基,甲酰基,羧基和它的酯和盐,氨基甲酰基,磺基和它的酯和盐,氨磺酰基,硝基,氨基,苯基,C1-C14-烷基,C1-C5-烷氧基,羰基-C1-C5-烷基,芳基-C1-C5-烷基;该氨基甲酰基,氨磺酰基和氨基可进一步是未取代的或被取代基R10取代一次或两次;该苯基可进一步是未取代的或被一个或多个取代基R10所取代;这些C1-C14-烷基,C1-C5-烷氧基,羰基-C1-C5-烷基,和芳基C1-C5-烷基可以是饱和的或不饱和的,分支的或不分支的,并且可进一步是未取代的或被一个或多个取代基R10取代;
取代基R10表示下面基团中的任何基团:卤素,羟基,甲酰基,羧基和它的酯和盐,氨基甲酰基,磺基和它的酯和盐,氨磺酰基,硝基,氨基,苯基,氨基烷基,哌啶子基,哌嗪基,吡咯烷子基,C1-C5-烷基,C1-C5-烷氧基;该氨基甲酰基,氨磺酰基和氨基可进一步是未取代的或被羟基、C1-C5烷基,C1-C5烷氧基取代一次或两次;该苯基可进一步被一个或多个以下基团所取代:卤素,羟基,氨基,甲酰基,羧基和它的酯和盐,氨基甲酰基,磺基和它的酯和盐,和氨磺酰基;该C1-C5烷基和C1-C5烷氧基可进一步是饱和的或不饱和的,分支或不分支的,并且可以进一步被以下基团中的任何基团取代一次或两次:卤素,羟基,氨基,甲酰基,羧基和它的酯和盐,氨基甲酰基,磺基和它的酯和盐,和氨磺酰基;
或在该通式中,取代基R1-R9中的两个可一起形成基团-B-,其中B表示下列基团中的任何一种:(-CHR10-N=N-),(-CH=CH-)n,(-CH=N-)n,或(-N=CR10-NR11-),其中n表示1-3的整数,R10是以上所定义的取代基,R11与R10定义相同。
4.根据权利要求1的方法,其中该含水介质另外包括下式Ⅱ的增强剂:
在该式中A是基团如-D,-CH=CH-D,-CH=CH-CH=CH-D,-CH=N-D,-N=N-D,或-N=CH-D,其中D选自-CO-E,-SO2-E,-N-XY和-N+-XYZ,其中E可以是-H,-OH,-R或-OR,X和Y和Z可相同或不同并选自-H和-R;R是C1-C16烷基,优选C1-C8烷基,该烷基可以是饱和的或不饱和的,分支的或不分支的,并可任意性地被羧基、磺基或氨基取代;B和C可相同或不同,并选自CmH2m+1;1fmf5.
5.根据权利要求1的方法,其中含水介质另外包括选自pHBS,pHBA,香草醛,香豆酸和肉桂酸的增强剂。
6.根据权利要求1的方法,其中含水介质另外包括选自N-羟基苯并三唑,紫尿酸,N-羟基乙酰苯胺和TEMPO的增强剂。
7.根据权利要求1-6中任何一项的方法,其中多糖是纤维素或淀粉。
8.根据权利要求1-7中任何一项的方法,其中该特性改变是强度提高和/或染色能力改变和/或柔软度提高和/或润湿性提高和/或无褶皱和/或阻燃性和/或拒水性和/或表面电荷改变和/或结晶性改变。
9.根据权利要求1-8中任何一项的方法,其中酚氧化酶是过氧化物酶。
10.根据权利要求9的方法,其中过氧化物酶是辣根过氧化物酶,大豆过氧化物酶,或可从鬼伞例如灰盖鬼伞或长根鬼伞,或从芽孢杆菌例如短小芽孢杆菌,或从粘球菌例如变绿粘球菌获得的过氧化物酶。
11.根据权利要求1的方法,其中过氧化氢源是过氧化氢或过氧化氢前体,例如过硼酸盐或过碳酸盐,或可产生过氧化氢的酶体系,例如氧化酶和它的底物,或过羧酸或它的盐。
12.根据权利要求11的方法,其中含水介质含有H2O2或H2O2的前体,其浓度相当于0.001-25mM H2O2。
13.根据权利要求1的方法,其中酚氧化酶是漆酶。
14.根据权利要求13的方法,其中漆酶可从栓菌例如绒毛栓菌,鬼伞例如灰盖鬼伞,或毁丝霉例如嗜热毁丝霉获得。
15.根据权利要求1的方法,其中酚氧化酶的浓度相当于0.01-100mg酶蛋白/g寡糖或多糖。
16.根据权利要求1的方法,其中含水介质中的增强剂以0.01-100mmol/g寡糖或多糖的浓度存在。
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- 1998-12-18 BR BR9813670-4A patent/BR9813670A/pt not_active IP Right Cessation
- 1998-12-18 CN CN98812431A patent/CN1309719A/zh active Pending
- 1998-12-18 WO PCT/DK1998/000563 patent/WO1999032652A1/en not_active Application Discontinuation
- 1998-12-18 JP JP2000525569A patent/JP2003521220A/ja active Pending
- 1998-12-18 EP EP98962291A patent/EP1040199A1/en not_active Withdrawn
- 1998-12-23 US US09/221,009 patent/US6087135A/en not_active Expired - Fee Related
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1999
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2000
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN104745662A (zh) * | 2015-04-20 | 2015-07-01 | 天津科技大学 | 一种漆酶-tempo体系氧化壳聚糖制备透明质酸替代物方法 |
Also Published As
Publication number | Publication date |
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CA2315109A1 (en) | 1999-07-01 |
JP2003521220A (ja) | 2003-07-15 |
PL341373A1 (en) | 2001-04-09 |
US6087135A (en) | 2000-07-11 |
WO1999032652A1 (en) | 1999-07-01 |
MXPA00005834A (es) | 2001-02-28 |
TR200001962T2 (tr) | 2001-01-22 |
KR20010024767A (ko) | 2001-03-26 |
BR9813670A (pt) | 2000-10-10 |
US6660503B2 (en) | 2003-12-09 |
US6346401B1 (en) | 2002-02-12 |
US20010055794A1 (en) | 2001-12-27 |
EP1040199A1 (en) | 2000-10-04 |
AU1751399A (en) | 1999-07-12 |
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