Article(id=1276616218010321014, tenantId=1146029695717560320, journalId=1235980609244409860, issueId=1276616049617408127, articleNumber=null, orderNo=null, doi=10.3969/j.issn.1000-2561.2025.08.019, pmid=null, cstr=null, oa=null, hot=null, price=null, onlineType=0, articleFormat=0, articleType=null, articleTypeStr=null, receivedDate=1742227200000, receivedDateStr=2025-03-18, revisedDate=null, revisedDateStr=null, acceptedDate=1746547200000, acceptedDateStr=2025-05-07, onlineDate=1782298624756, onlineDateStr=2026-06-24, pubDate=1756051200000, pubDateStr=2025-08-25, doiRegisterDate=null, doiRegisterDateStr=null, onlineIssueDate=1782298624756, onlineIssueDateStr=2026-06-24, onlineJustAcceptDate=null, onlineJustAcceptDateStr=null, onlineFirstDate=null, onlineFirstDateStr=null, sourceXml=null, magXml=null, createTime=1782298624756, creator=13701087609, updateTime=1782298624756, updator=13701087609, issue=Issue{id=1276616049617408127, tenantId=1146029695717560320, journalId=1235980609244409860, year='2025', volume='46', issue='8', pageStart='1785', pageEnd='2029', issueExtLink='null', onlineDate='null', pubDate='1756051200000', pubDateStr='2025-08-25', beforeIssueId=null, nextIssueId=null, price=null, status=1, issueComplete=1, articleOrder=1, issueType=-1, specialIssue=null, createTime=1782298584608, creator='13701087609', updateTime=1782298660748, updator='13701087609', preIssue=null, nextIssue=null, articleTotal=null, ext={EN=IssueExt(id=1276616369089147039, tenantId=1146029695717560320, journalId=1235980609244409860, issueId=1276616049617408127, language=EN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=), CN=IssueExt(id=1276616369089147040, tenantId=1146029695717560320, journalId=1235980609244409860, issueId=1276616049617408127, language=CN, specialIssueTitle=, coverIllustrator=null, specialIssueEditor=, specialIssueAbout=)}, issueFiles=null, downloadFileDto=null}, startPage=1967, endPage=1977, ext={EN=ArticleExt(id=1276616218421362808, articleId=1276616218010321014, tenantId=1146029695717560320, journalId=1235980609244409860, language=EN, title=Research Progress on Resource Utiliza tion of Natural Rubber Serum, columnId=1236286112713470633, journalTitle=Chinese Journal of Tropical Crops, columnName=Post-harvest Treatment & Quality Safety, runingTitle=null, highlight=null, articleAbstract=

Natural rubber serum (NRS), a by-product generated during the processing of natural rubber (NR), contains all essential plant nutrients and numerous high-value bioactive components such as quebrachitol, ergothioneine, glutathione, and functional proteins, demonstrates significant resource utilization potential. Effective exploitation of NRS can not only mitigate environmental pollution and reduce disposal costs but also extend the NR industrial chain and enhance the economic benefits of the NR industry. In recent years, technological innovations in membrane separation, crystallization purification, fermentation, and biological extraction have facilitated substantial progress in the resource utilization of NRS. This paper systematically reviewed the component characteristics of NRS and advances in its application in multiple fields. It detailed the research and utilization of plant-derived nutrients in NRS, with a focus on the application progress of its bioactive components in high-value fields such as biomedicine and cosmetics. Finally, prospects for future applications were discussed, aiming to provide references for related research and support the green transformation and sustainable development of the NR industry.

, authors=null, authorsList=Shikuan JIANG, Guimei ZHANG, li YAN, Rong XU, authorCompany=null, correspAuthors=Guimei ZHANG, authorNote=null, correspAuthorsNote=null, copyrightStatement=null, copyrightOwner=null, extLink=null, articleAbsUrl=null, sourceXml=null, magXml=null, pdfUrl=null, pdf=null, pdfFileSize=null, pdfExtLink=null, richHtmlUrl=null, mobilePdfUrl=null, reviewReport=null, pdfFirstPage=null, abstractGraph=null, abstractGraphContent=null, abstractVideo=null, citation=null, cebUrl=null, magXmlContent=null, mapNumber=null, fund=null), CN=ArticleExt(id=1276616219172143226, articleId=1276616218010321014, tenantId=1146029695717560320, journalId=1235980609244409860, language=CN, title=天然橡胶乳清资源化利用研究进展, columnId=1236286112877048492, journalTitle=热带作物学报, columnName=采后处理与质量安全, runingTitle=null, highlight=null, articleAbstract=

天然橡胶乳清(NRS)是天然橡胶(NR)加工产生的副产物,含有植物所需的全部营养成分及白坚木皮醇、麦角硫因、谷胱甘肽、活性蛋白等众多高附加值活性成分,具有较高的资源化利用潜力。若能有效开发利用,既减少环境污染和处理成本,又延长NR产业链,提高NR产业经济效益。近年来,通过膜分离、结晶提纯、发酵及生物提取等技术创新,NRS的资源化利用取得重要进展。本研究系统综述NRS的成分特征及其在多个领域的应用研究进展。阐述NRS中植物营养成分的研究利用状况,并重点介绍NRS中活性成分在生物医药和化妆品等高值化利用领域的应用研究进展。最后,对其应用前景进行展望,旨在为相关研究提供参考,助力NR产业绿色转型及可持续发展。

, authors=

姜士宽(1983—),男,学士,副研究员,研究方向:天然橡胶乳清的高值化利用。

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* 张桂梅(ZHANG Guimei),E-mail:
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姜士宽(1983—),男,学士,副研究员,研究方向:天然橡胶乳清的高值化利用。

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姜士宽(1983—),男,学士,副研究员,研究方向:天然橡胶乳清的高值化利用。

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Preparation method and application of natural rubber serum fermentation product extract: CN202110437063.3[P]. 2022-10-25. (in Chinese), articleTitle=Preparation method and application of natural rubber serum fermentation product extract, refAbstract=null), Reference(id=1276616253565436179, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276616218010321014, doi=null, pmid=null, pmcid=null, year=2021, volume=126, issue=null, pageStart=null, pageEnd=null, url=null, language=null, rfNumber=[78], rfOrder=100, authorNames=GUERRA N B, PEGORIN G S, BORATTO M H, DE BARROS N R, DE OLIVEIRA GRAEFF C F, HERCULANO R D, journalName=Materials Science & Engineering, C: Materials for Biological Applications, refType=null, unstructuredReference=GUERRA N B, PEGORIN G S, BORATTO M H, DE BARROS N R, DE OLIVEIRA GRAEFF C F, HERCULANO R D. Biomedical applications of natural rubber latex from the rubber tree Hevea brasiliensis[J]. Materials Science & Engineering, C: Materials for Biological Applications, 2021, 126: 112126., articleTitle=Biomedical applications of natural rubber latex from the rubber tree Hevea brasiliensis, refAbstract=null), Reference(id=1276616253636739348, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276616218010321014, doi=null, pmid=null, pmcid=null, year=1994, volume=5, issue=9, pageStart=647, pageEnd=650, url=null, language=null, rfNumber=[79], rfOrder=101, authorNames=CIAPETTI G, STEA S, PIZZOFERRATO A, CHECCHI L, PELLICCIONI G A, journalName=Journal of Materials Science Materials in Medicine, refType=null, unstructuredReference=CIAPETTI G, STEA S, PIZZOFERRATO A, CHECCHI L, PELLICCIONI G A. A latex membrane, as an alternative device in the GTR technique: preliminary report on its biocompatibility[J]. 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Amino acid content in the spray-dried powder

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氨基酸Amino acid含量Content/%占比Ratio/%
天冬氨酸4.06614.97
谷氨酸3.39612.50
丙氨酸1.1264.14
甘氨酸1.4595.37
缬氨酸0.8993.31
亮氨酸2.0317.48
丝氨酸2.2298.21
赖氨酸1.7276.36
苏氨酸1.1904.38
半胱氨酸2.0127.41
精氨酸1.4015.16
脯氨酸1.7186.32
异亮氨酸0.7112.62
酪氨酸1.6686.14
苯丙氨酸0.7632.81
组氨酸0.7652.82
), ArticleFig(id=1276616230731645086, tenantId=1146029695717560320, journalId=1235980609244409860, articleId=1276616218010321014, language=CN, label=表1, caption=

喷雾干燥粉中氨基酸含量

, figureFileSmall=null, figureFileBig=null, tableContent=
氨基酸Amino acid含量Content/%占比Ratio/%
天冬氨酸4.06614.97
谷氨酸3.39612.50
丙氨酸1.1264.14
甘氨酸1.4595.37
缬氨酸0.8993.31
亮氨酸2.0317.48
丝氨酸2.2298.21
赖氨酸1.7276.36
苏氨酸1.1904.38
半胱氨酸2.0127.41
精氨酸1.4015.16
脯氨酸1.7186.32
异亮氨酸0.7112.62
酪氨酸1.6686.14
苯丙氨酸0.7632.81
组氨酸0.7652.82
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天然橡胶乳清资源化利用研究进展
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姜士宽 , 张桂梅 * , 岩利 , 徐荣
热带作物学报 | 采后处理与质量安全 2025,46(8): 1967-1977
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热带作物学报 |采后处理与质量安全 2025 , 46 (8) : 1967 -1977
天然橡胶乳清资源化利用研究进展
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姜士宽(1983—),男,学士,副研究员,研究方向:天然橡胶乳清的高值化利用。

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姜士宽, 张桂梅* , 岩利, 徐荣
作者信息
  • 云南省热带作物科学研究所/云南省天然橡胶可持续利用研究重点实验室(筹)/天然橡胶良种选育与栽培技术国家地方联合工程研究中心,云南景洪 666100
通讯作者:
* 张桂梅(ZHANG Guimei),E-mail:
Research Progress on Resource Utiliza tion of Natural Rubber Serum
Shikuan JIANG, Guimei ZHANG* , li YAN, Rong XU
Affiliations
  • Yunnan Institute of Tropical Crops / Yunnan Key Laboratory of Sustainable Utilization Research on Rubber Tree / National and Local Joint Engineering Research Center of Breeding and Cultivation Technology of Rubber Tree, Jinghong, Yunnan 666100, China
出版时间: 2025-08-25 doi: 10.3969/j.issn.1000-2561.2025.08.019
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天然橡胶乳清(NRS)是天然橡胶(NR)加工产生的副产物,含有植物所需的全部营养成分及白坚木皮醇、麦角硫因、谷胱甘肽、活性蛋白等众多高附加值活性成分,具有较高的资源化利用潜力。若能有效开发利用,既减少环境污染和处理成本,又延长NR产业链,提高NR产业经济效益。近年来,通过膜分离、结晶提纯、发酵及生物提取等技术创新,NRS的资源化利用取得重要进展。本研究系统综述NRS的成分特征及其在多个领域的应用研究进展。阐述NRS中植物营养成分的研究利用状况,并重点介绍NRS中活性成分在生物医药和化妆品等高值化利用领域的应用研究进展。最后,对其应用前景进行展望,旨在为相关研究提供参考,助力NR产业绿色转型及可持续发展。

天然橡胶乳清  /  资源化利用  /  麦角硫因  /  FrHB1蛋白

Natural rubber serum (NRS), a by-product generated during the processing of natural rubber (NR), contains all essential plant nutrients and numerous high-value bioactive components such as quebrachitol, ergothioneine, glutathione, and functional proteins, demonstrates significant resource utilization potential. Effective exploitation of NRS can not only mitigate environmental pollution and reduce disposal costs but also extend the NR industrial chain and enhance the economic benefits of the NR industry. In recent years, technological innovations in membrane separation, crystallization purification, fermentation, and biological extraction have facilitated substantial progress in the resource utilization of NRS. This paper systematically reviewed the component characteristics of NRS and advances in its application in multiple fields. It detailed the research and utilization of plant-derived nutrients in NRS, with a focus on the application progress of its bioactive components in high-value fields such as biomedicine and cosmetics. Finally, prospects for future applications were discussed, aiming to provide references for related research and support the green transformation and sustainable development of the NR industry.

natural rubber serum  /  resource utilization  /  ergothioneine  /  FrHB1 protein
姜士宽, 张桂梅, 岩利, 徐荣. 天然橡胶乳清资源化利用研究进展. 热带作物学报, 2025 , 46 (8) : 1967 -1977 . DOI: 10.3969/j.issn.1000-2561.2025.08.019
Shikuan JIANG, Guimei ZHANG, li YAN, Rong XU. Research Progress on Resource Utiliza tion of Natural Rubber Serum[J]. Chinese Journal of Tropical Crops, 2025 , 46 (8) : 1967 -1977 . DOI: 10.3969/j.issn.1000-2561.2025.08.019
天然橡胶(natural rubber,NR)作为关键工业基础材料及战略储备资源,与石油、钢铁及煤炭共同被列为四大基础工业原料。在NR生产加工过程中,副产物天然橡胶乳清(natural rubber serum,NRS)呈规模化产出,因其具有复杂的化学组分(包含高浓度有机化合物及氨氮化合物),现主要被纳入有机废水管理体系进行生物降解处理[1]。然而,其成分分析表明,NRS中富含功能性蛋白质、氨基酸复合物及糖类衍生物等多种生物活性成分[2]。现行污水处理模式不仅需要投入高额的处理成本,更造成资源的浪费。针对这一资源错配问题,学界早于20世纪90年代即启动了对其高值化利用的研究,着力于生化活性物质的回收技术开发[3]。研究表明,NRS具有多层级开发潜力:在初级资源化利用层面,可制备农用肥料等基础产品;而在高值化利用维度,依托现代分离纯化技术可从中提取白坚木皮醇、麦角硫因及活性蛋白等高附加值生物活性物质。此类组分在精细化妆品原料开发及生物医药领域展现出较高的应用价值[4-5]
本研究系统综述NRS的成分特性及其在工业、农业、生物医药、化妆品等领域的应用研究进展。首先,深入解析NRS中诸如白坚木皮醇、蛋白质、麦角硫因等活性成分与功能特性;继而,从灌溉施肥、有机肥料制备、微生物培养基开发、沼气发酵等多个角度对NRS的初级资源化利用现状进行总结;随后,重点探讨其在抗癌、抗真菌、抗氧化、促进伤口愈合等生物医药领域及美白、抗衰老等化妆品领域的创新应用;最后,对NRS的资源化利用前景进行展望,并结合市场需求、研究开发现状,深入分析NRS在未来实现高值化利用的途径。
天然胶乳是橡胶粒子分散在水中的胶体,其中水相部分称为乳清,占胶乳的60%~70%(w/w)。乳清由水和非胶组分组成,非胶组分约占胶乳质量的5%(w/w),包括肌醇2.38%(w/w)、蛋白质1.10%、糖类0.40%、游离氨基酸0.13%、抗坏血酸0.03%、含氮碱类0.06%、谷胱甘肽0.02%等[6]
白坚木皮醇是一种左旋的天然手性化合物,化学式为C7H14O6,因其光学特性备受关注,它可以作为手性源合成各种光学活性药物,用于抗生素、抗氧化、酶抑制剂、抑制血管增生、治疗糖尿病和艾滋病等[7]。白坚木皮醇在不少植物中被分离发现,如夹竹桃科植物、无患子科植物等,但含量普遍很低,NRS是白坚木皮醇最富集的生物质来源,含量可达1.5%(w/w[8],是当前最具产业化潜力的生物提取基质。
1930年,LEVI[9]和MCGAVACK等[10]报道了从乳清中提取白坚木皮醇,首先将胶乳喷雾干燥得到固体粉末,然后在热的乙醇中提取15~30 min,重复2~3次,再用骨炭脱色,然后过滤和浓缩,结晶得到白坚木皮醇。HART[11]采用离心或酸凝胶乳取得乳清,用石灰和加热的方式除去蛋白质,然后利用离子交换处理后减压浓缩,结晶得到白坚木皮醇。1991年UDAGAWA等[12]把浓缩胶乳干燥后溶解于甲醇中,减压蒸馏后经过结晶、活性炭脱色、重结晶、离子交换树脂、醇析等步骤得到白坚木皮醇。随后人们一直尝试各种方法从乳清中提取白坚木皮醇[13-15],但是这些方法都用到大量的有机溶剂,所用工艺主要包括柱层析和喷雾干燥,能耗高,效率低,不适合规模化生产。JIANG等[16]采用膜分离技术替代传统的蒸发浓缩和柱层析对NRS进行浓缩和除杂,结合结晶法提纯,开发出可规模化提取白坚木皮醇的工艺技术,产品纯度达到99%以上,经大鼠试验表明白坚木皮醇具有增加骨密度的功能[17]
新鲜胶乳中含有1%~2%的蛋白质,其中约20%的蛋白质分布于橡胶粒子表面,65%溶解于NRS中,其余部分则与胶乳底层组分相关联。NRS中至少包含15种功能蛋白(如α球蛋白、橡胶蛋白、纤维状结构蛋白及碱性蛋白质等),经分离、干燥后可制成蛋白质粉,富含多种氨基酸和磷脂,具有在工业蛋白质生产、动物饲料添加剂及微生物培养基制备等领域应用的潜力。
SHIODA等[18]采用乙酸凝固天然胶乳以去除橡胶烃,随后利用反渗透膜将乳清浓缩至固体含量达10%~30%。所得浓缩液含有多种蛋白质、氨基酸、维生素和糖类等成分,可作为肥料、表面处理剂等产品的原料。ISMAIL等[19]采用膜分离技术将NRS中的蛋白质与糖类分离,再经喷雾干燥制备蛋白质粉末。该蛋白质粉末含有多种氨基酸,含量如表1所示,其中天冬氨酸含量最高,约占总氨基酸的15%,其次是谷氨酸,此工艺已成功完成中试生产。近期,ISMAIL等[20]进一步研究了将上述方法制备的蛋白干粉添加到肉鸡基础日粮中的可行性。研究结果表明,在肉鸡饲料中添加4%的NRS蛋白对肉鸡的生长性能最为理想,且不会对肠道形态和盲肠细菌产生不良影响。研究结论表明,NRS蛋白可作为肉鸡饲料成分的可行替代品。
麦角硫因是一种稀有的天然含硫氨基酸类强抗氧化剂,具有独特的氧化还原机制[21],在生理pH环境下相较于其他抗氧化剂更为稳定,不易发生自发氧化[22]。其生物活性广泛,涵盖清除自由基、美白肌肤、延缓衰老、防止紫外线辐射损伤、维持DNA合成与细胞正常生长等方面。然而,EGT的生物合成仅限于部分微生物,如放线菌、链霉菌、蕈菌以及某些蓝细菌,植物和动物自身并不具备合成EGT的能力,只能通过外部摄取来满足需求[23]
早在20世纪60年代,TAN等[24]学者便已发现橡胶树胶乳中含有EGT,100 mL鲜胶乳中含量为12~17 mg。后续,ARCHER等[25]研究表明,C乳清中EGT的含量相对较低,主要集中在胶乳的底层部分,且不同地域来源的胶乳中EGT含量差异显著,100 mL鲜胶乳中EGT含量的波动范围为0~48 mg。SOYSUWAN[26]通过喷雾干燥的方法制备乳清干粉,并评估了其对DPPH自由基的清除能力,证实该乳清干粉具有抗氧化活性。将NRS通过凝胶过滤进一步纯化含硫醇的抗氧化剂,所得提取物的抗氧化活性显著增强,其中利用1000 Da超滤透过液制备的乳清干粉中EGT含量达到1.18 mg/kg。此外,姜士宽等[27]采用2500 Da超滤膜处理乳清,随后对滤过液进行纳滤浓缩,再经离子交换树脂纯化,最终结晶得到纯度高达99.98%的EGT。
谷胱甘肽是一种含γ-酰胺键和巯基的三肽,由谷氨酸、半胱氨酸及甘氨酸组成,几乎存在于人体的每一个细胞[28],谷胱甘肽能帮助保持正常的免疫系统功能,并具有抗氧化作用、整合解毒作用。当人体组织细胞发生衰老、感染、中毒、氧化应激时,都可以使细胞内谷胱甘肽生物合成能力降低、含量下降。适时补充外源性谷胱甘肽可以预防、减轻、终止组织细胞的损伤,改变病理生理过程[29]。另外,谷胱甘肽还可作为功能性食品的基料,在延缓衰老、增强免疫力、抗肿瘤等功能性食品广泛应用[30]。ARCHER等[25]在100 g鲜胶乳中测出谷胱甘肽的含量为0.01 g,SREELATHA等[31]检测出在橡胶树的叶片和树皮中均含有谷胱甘肽,在1 kg新鲜叶片和树皮中,谷胱甘肽的含量分别为2.7~5.09 g和0.34~2.18 g。另外,在不同季节,高产树、低产树的树叶里谷胱甘肽的含量没有明显的差异,而高产树的树皮中谷胱甘肽含量总高于低产树。
NRS含有氮、磷、钾、氨基酸和有机酸等多种植物营养成分,而不含重金属等有毒物质[32-33],可以作为水肥资源、微生物培养基等,在工农业生产方面具有巨大的应用潜力。实现上述目的仅需简单、低成本的技术手段,且这类产品市场容量大,可以支撑起NRS的规模化开发利用。
农业灌溉是NRS资源化利用最早开发的途径之一。在马来西亚,已尝试运用NRS灌溉橡胶树、油棕树、水稻及豆科植物等多种作物[34]。在斯里兰卡,研究者探究了绉片乳清对幼龄橡胶树生长的影响,设置包括普通肥料、1/2肥料与NRS混合、NRS不稀释及NRS与水按不同比例稀释等多种处理方式。研究发现,经过20周后,所有经NRS处理的植株在树高和树粗生长方面均得到显著改善[35]。KANTACHOTE等[36]利用紫色非硫细菌和菠萝发酵提取物在微好氧光照条件下对NRS进行处理,并用于水稻种子发芽试验。结果显示,未稀释废水及稀释倍数在1∶25~1∶200之间的废水均未表现出植物毒性,与蒸馏水相比,制胶废水反而促进了水稻种子的萌发,这可能是由于处理过的NRS通过提供营养物质刺激了种子的发芽过程。
近年来,随着国内环保要求的日益严格,对NRS的处理与再利用问题再次引起广泛关注。邢巧等[37]研究发现,10%浓度稀释的胶清废水、50%的厌氧出水及好氧处理终水对芫荽生产具有显著的促进作用,效果均优于复合肥。这表明胶清废水和厌氧出水在经过适当稀释和pH调整后,可用于农作物灌溉;好氧处理终水则可直接用于灌溉。杨燕[38]、延晓惠[39]等开展关于胶清废水作为农业水肥资源的研究,发现胶清液对小白菜、生菜、苋菜、辣椒等作物的生长和品质均具有良好的促进作用,并可进一步加工成胶清基液肥。研究结果表明,胶清基液肥在适宜浓度下对小白菜和生菜种子的萌发具有积极的促进作用,但若浓度过高,则可能对种子产生一定的负面影响。此外,胶清液对土壤性质具有良好的改良作用,可进一步加工成胶清基土壤改良剂。研究建议,在使用胶清液时,可添加3%的尿素制成胶清基液肥,并在适当稀释后可直接用于灌溉作物。
氮肥和灌溉已被证实是影响橡胶树生长、产量和质量的2个关键因素[40]。制胶废水中的营养成分源自橡胶树,经处理后回用于水肥管理,能够有效增加橡胶树的产胶量,实现资源的循环利用。然而,频繁使用制胶废水灌溉可能导致橡胶树出现落叶、疫霉病等问题,同时,废水中高氮含量还可能加重橡胶树的风害,以及导致水稻空粒率增加[41]。因此,制胶废水的合理利用不仅能够提高作物产量、减少化肥使用、降低废水处理成本,还能实现环境效益与经济效益的双赢。但为了确保废水利用的安全性和有效性,需要根据制胶废水中所含的营养成分,结合当地的气候条件、土壤类型、种植作物的种类及其生长期等因素,进行科学的灌溉试验,以确定最为适宜的灌溉方法和管理策略[42]
田岛义夫[43]采用喷雾干燥技术处理NRS,成功制备出粒径介于10~100 μm的颗粒状物质,该物质具有作为橡胶添加剂及饲料添加剂的潜在应用价值。日本横滨橡胶有限公司与马来西亚橡胶研究所联合开发一种创新的乳清利用技术,该技术首先对NRS进行浓缩处理,随后依据其成分含量精确添加其他养分,从而生产有机肥料。这一科研成果直接促成了全球首家NRS肥料厂的建立[44]。目前,该工厂已实现化肥的商业化生产,并成功从乳清中提取出多种有用物质。所生产的有机肥料不仅在日本国内广泛应用于蔬菜、果树、花卉以及高尔夫球场草坪的养护,还远销至多个国家。
经乳清制备的肥料富含氮、磷、钾等基础营养元素,同时特别含有独特的糖类和蛋白质成分。这些特定的糖类和蛋白质不仅能够显著促进植物对氮、磷的吸收利用,还能有效增强植物对钾的吸收效率。此外,它们还能够刺激水果中糖分的合成与积累,从而显著改善水果的口感和风味。该肥料完全符合环保标准,在日本的高尔夫球场上也得到了广泛的应用和推广。
微生物培养过程中,通常需要多种营养物质,如氨基酸、维生素和矿物质等。NRS含有丰富的营养成分,可作为发酵培养基的关键组分,用于细菌、酵母和藻类的培养。NRS制备的干粉通常含有16.5%的可溶性含氮化合物、28%的可溶性无氮化合物、18%的灰分和2%的水分。研究表明[45],NRS粉能够促进多种微生物的生长,尤其对厌氧菌具有显著的促生长效果,可提供与酵母提取物相当的营养支持。此外,在含有酵母提取物、肉提取物和酪蛋白等营养物质的培养基中,NRS粉与这些营养物质之间存在协同作用,进一步增强微生物的生长和代谢。
华南热带作物产品加工设计研究所[46]已成功利用NRS作为微生物发酵培养基,用于培养白地霉、啤酒酵母等单细胞蛋白质,作为蛋白饲料用于家畜饲养,取得了良好的效果。
双歧杆菌是健康人体肠道菌群的重要组成部分,能够有效抑制多种有害细菌的生长,其中两歧双歧杆菌是肠道双歧杆菌中普遍存在的一种,广泛应用于食品工业。研究表明,健康婴儿定期摄入两歧双歧杆菌,可在一定程度上预防肠道感染的发生。OIKI等[47]和ETOH等[48]研究发现,NRS粉对两歧双歧杆菌具有显著的生长刺激作用,向培养基中添加NRS粉能够提高代谢物的产量和生产效率。铵盐作为NRS粉的主要成分之一,作为氮源有助于菌株的生长,而NRS粉中的其他活性成分也可能具有附加的营养作用。从NRS粉中提纯出的一种十肽,对两歧双歧杆菌具有显著的生长刺激作用,其比活性提高了53倍,提取率为1.3%。
NRS富含有机物质,是沼气发酵的优质原料。20世纪80年代,贺鹰抟等[49]利用NRS进行沼气发酵的研究。乳清中挥发酸含量较高,产甲烷微生物可直接将醋酸转化为甲烷。与其他发酵原料如秸秆、牲畜粪便相比,NRS具有产气迅速且甲烷含量高(60%)的优势,每吨NRS可产8~10 m3沼气(以含55%甲烷计)。
方日明等[50]开展了标准胶废水厌氧处理制取沼气的生产性试验。研究表明,每吨标准胶废水(NRS)可产生含甲烷60%以上的沼气约30 m3,相当于约15 kg燃料油的热量。利用标准胶废水制取沼气在技术和经济上均具有可行性,且随着生产规模的扩大,其经济效益将更加显著,同时还能有效减轻废水对环境水域的污染。经测定,沼气发酵后的橡胶废水中氮、磷、钾含量分别为800~1000、80~110、1000~1200 mg/L,可作为水肥用于农业生产[51]
除含有氮、磷、钾等植物营养成分外,NRS还富含多种生物活性成分。在利用这些活性成分时,有的通过提取出单一化合物,有的则以混合组分的形式加以利用。与仅利用植物营养成分相比,显然这些活性成分的附加值更高,但同时成本和技术难度也更大,产业化开发过程更为复杂。
YANG等[52]研究了天然胶乳B乳清对人乳腺癌上皮细胞系MCF-7及MDAMB231的特异性抗增殖作用,结果表明,B乳清及B乳清透析沉淀物(透析袋截留分子量3000 Da)对癌源细胞MDA-MB231表现出特异性抗增殖活性,但对非癌源细胞影响甚微,研究结果显示B乳清透析沉淀物在癌症治疗领域具有潜在应用价值。ONG等[53]利用乳清做细胞毒性实验发现,B乳清和C乳清可以拟制癌细胞系(Hela)的生长,据此首次提出乳清在癌症治疗药物方面的潜在应用。据报道[52,54-55],胶乳B乳清和C乳清都能够在不影响非癌源细胞系生长的情况下,表现出针对癌细胞系的特定抗增殖活性,B乳清能够消灭乳腺癌来源细胞系(即MDA-MB231)的生长,C乳清可抑制肝癌细胞系HepG2的生长。但当B乳清和C乳清预热后,抑制癌源细胞增殖的活性则显著降低甚至丧失,推测乳清中抑制癌源细胞增殖的活性物质是受热会失去活性的蛋白质。
橡胶树在采集胶乳过程中,几乎每2~3 d就会遭受机械损伤。基于这一现象,研究人员推测橡胶树可能含有一些具有抗菌能力的物质,以在流胶过程中抵御细菌的入侵[56]。后续研究发现,胶乳中的一些蛋白质,如橡胶蛋白、几丁质酶和溶菌酶等,与抗菌作用密切相关。
CHURNGCHOW等[57]从天然胶乳底层部分的黄色体中分离出2种β-1,3-葡聚糖酶同工酶GI和GII,这些酶参与橡胶树对病原体的防御反应。通过离子交换色谱法对这2种酶进行纯化和表征,研究发现随着割胶频率的增加,这些酶的含量会显著上升。研究结果还表明,葡聚糖酶GII在巴西橡胶树中具有最高的抗真菌活性。
PARIJS等[58]的研究表明,橡胶蛋白(hevein)对多种真菌具有抑制作用,包括偃麦草核腔菌、灰霉菌、颖枯壳针孢、黄色镰孢菌、尖孢镰刀菌、布拉克须霉和稻瘟病菌等。KANOKWIROON等[59]也证实,橡胶蛋白是一种富含高浓度半胱氨酸的蛋白质,对白色念珠菌、热带念珠菌和克鲁塞念珠菌等不同微生物具有优异的抗菌活性。由此可以推断,富含大量橡胶蛋白的NRS具有良好的抗菌特性。DARULIZA等[60-61]的研究进一步表明,C乳清对黑曲霉菌具有特定的抗菌活性,而B乳清则对白色念珠菌表现出抗菌效果。此外,盐水虾毒性试验表明,NRS无毒性。因此,NRS可用于生产特定的抗真菌剂,具有广阔的应用前景。
自20世纪70年代起,科学家们在天然胶乳中发现了一系列具有强大抗氧化性能的天然抗氧化剂[62]。这些抗氧化剂主要包括磷脂类化合物、氨基酸、酚类化合物、生育三烯酚和甜菜碱等,其化学性质各异,既有水溶性也有脂溶性,其中水溶性抗氧化剂主要存在于NRS中。
SIRIWONG等[63]采用己烷、三氯甲烷、甲醇等多种有机溶剂,从新鲜胶乳干胶膜中提取抗氧化物质,并通过总酚含量测定、铁离子还原抗氧化能力评估及清除DPPH(1,1-二苯基-2-三硝基苯肼)活性分析等方法综合评价其抗氧化活性。研究发现,以氯仿与甲醇按体积比4∶1配制的混合溶剂提取的干胶膜提取物展现出最高的抗氧化活性。
KERCHE-SILVA等[64]对巴西橡胶树天然胶乳中的C乳清进行了深入的抗氧化特性研究。将新鲜胶乳通过离心分离得到C乳清,并采用磷钼酸盐法对其体外清除自由基的能力进行测定。结果显示,C乳清能够有效清除多种活性氧自由基,包括羟基自由基、一氧化氮自由基和过氧化氢,并表现出与抗坏血酸相当的抗氧化能力。此外,C乳清的细胞毒性评估试验表明,其细胞毒性具有细胞系依赖性。具体而言,对于来源于皮肤成纤维细胞的CCD 1059sk细胞系,C乳清未表现出细胞毒性。这些研究成果为C乳清在治疗与活性氧相关的皮肤病及皮肤预防药物制剂领域的潜在应用提供科学依据。
据推测,C乳清的自由基清除活性可能与其天然含有的多种抗氧化剂密切相关,如硫醇、抗坏血酸盐、γ-生育三烯酚、植物甾醇、磷脂、酚类化合物、甜菜碱、蛋白质和氨基酸等[65]
科学家以巴西橡胶树天然胶乳为基体,成功制备出一种生物膜,研究发现其能够促进伤口愈合、狗食道壁再生以及兔结膜再生,其作用机理主要通过促进血管再生和细胞粘附等途径实现[66-68]。利用鸡胚绒毛尿囊膜实验和兔耳皮肤溃疡模型对NRS组分的血管生成活性和伤口愈合活性进行测定,结果显示NRS组分具有明显的促进血管生成作用,能够有效增强血管通透性,并且显著加速伤口愈合。这些结果与使用天然乳胶生物膜进行临床试验所得的促进伤口愈合结果相一致。此外,经过煮沸或蛋白酶处理后的NRS组分失去了这些生物活性,表明其活性主要来源于乳清中的多肽结构物质[68]
在一项涉及107名慢性中耳炎患者的临床试验中,天然胶乳生物膜作为临时植入物用于鼓膜再生术,并与商品硅胶膜进行了对比。研究结果表明,天然胶乳生物膜与人类鼓膜组织具有良好的生物相容性,能够诱导比硅胶膜更显著的移植血管化,且在试验期间未出现毒性或过敏反应[69]。这些研究均表明天然胶乳中含有促进伤口愈合和血管生成的成分。LEITE等[70]研究了NRS对实验性皮肤擦伤模型的愈合作用,发现天然乳胶能够促进角质形成细胞在体外的迁移和增殖,并显著加速动物表皮损伤模型的伤口愈合,1% NRS在促进大鼠擦伤皮肤愈合以及表皮细胞再生方面,效果优于抗菌药物(二葡萄糖酸氯己定10 mg/mL)和生理盐水。
NRS蛋白由3个主要组分构成,即FrHB1蛋白(F1)、FrHB2蛋白(F2)和FrHB3蛋白(F3),这些组分可直接与细胞和活体组织相互作用,在组织再生过程中发挥着关键作用,尤其是F1蛋白组分在促进血管生成方面效果显著[71]。DIAS等[72]从醋酸凝固的天然胶乳中分离出乳清,并进一步提取了F1蛋白组分,用于大鼠坐骨神经挤压型损伤试验。结果显示,在坐骨神经损伤的治疗中,F1蛋白组分的再生效果优于单独的激光治疗。MORAIS等[73]在体内模型中比较了F1蛋白和NRS的伤口愈合潜力,结果显示,二者均能显著刺激成纤维细胞的增殖,其中0.01%的F1蛋白浓度可使细胞增殖增加(47.1±11.3)%。
综上所述,NRS中富含能够诱导新生血管和组织生长的活性物质,这些物质不仅不会引起宿主排斥反应,还能增强血管通透性并加速伤口愈合。鉴于NRS来源广泛且成本低廉,其作为一种应用潜力巨大的生物材料,有望在组织再生领域发挥重要作用。
ARCHER等[25]对NRS的成分进行了系统性研究总结,并得到后续学者的不断完善补充。经分析,NRS中富含多种功效成分,如EGT、谷胱甘肽、抗坏血酸、游离氨基酸、β-葡聚糖、果酸(柠檬酸、苹果酸)、辅酶Ⅰ、辅酶Q10、超氧化物歧化酶等,这些功效成分在化妆品领域应用广泛。特别是EGT,能有效改善紫外线引起的皮肤损伤,增加紫外线照射后成纤维细胞的细胞活力,显著降低活性氧(ROS)的产生,促进Ⅰ型前胶原的合成,对紫外诱导的线粒体DNA损伤具有保护作用,是一种理想的护肤成分[74]。NRS中这些功效成分的组合存在,使得NRS近似一种天然的化妆品组合物。中国专利CN101204362A[75]公开了一种含有源自NRS提取物的皮肤美白成分,用截留分子量为10 kDa的超滤膜处理NRS,滤过液喷雾干燥,然后用丙酮溶液提取其中的丝氨酸蛋白酶抑制剂等小分子蛋白和肽,提取物具有诱导去除哺乳动物皮肤色素的效果,可用于皮肤美白产品中。国际专利WO2019/022679A1[76]公开了一种生发产品配方,NRS经超滤处理后喷雾干燥,获得的干粉进一步用丙酮、甲醇溶液提纯,提取物可用于促进头发生长的配方,或者和生发药物米诺地尔混合制成生发药膏。以上研究表明,NRS无论是成分还是功效都具备用于化妆品用途的潜力。姜士宽等[77]开展了NRS发酵产物提取物的研究,利用天然胶乳离心获得的胶清为原料,以大米作为补充碳源经过酵母菌发酵,制备的乳清发酵产物提取物中含有EGT、谷胱甘肽、β-葡聚糖、果酸(乳酸、柠檬酸、苹果酸等)、核苷酸、抗坏血酸、游离氨基酸、甘油、白坚木皮醇、矿物质等多种活性成分,完成了产品的斑贴测试和人体功效评价测试。斑贴测试表明,30例受试者无人出现皮肤不良反应;人体功效评价测试结果显示乳清发酵产物提取物具有保湿、控油的功效,皮肤颜色L值、b值、ITA°值、皮肤黑色素含量、Visia色斑面积占比与基础值相比均有显著性改善,表明具有美白、祛斑的作用。
长期以来,NRS被视为高浓有机废水,其处理设施占地面积大、投资及运行维护成本高昂,给橡胶加工厂带来沉重负担。此外,废水中蛋白质腐败产生的无组织恶臭废气,也引发了较大的社会舆论压力,加剧了企业的环保困境。因此,NRS的资源化利用一直是国内外研究热点,且研究方向正从初级资源化利用向高值化利用转变,但目前实现产品上市的研究仍属少数。
在已有的研究成果中,马来西亚Muhibbah Lateks Sdn Bhd公司基于NRS开发的Green Serum液体肥已成功上市,作为草坪、花园和农作物的天然有机微生物液体肥和叶面喷施肥。泰国生命科学卓越中心和宋卡王子大学联合开发了化妆品原料“Hb EXTRACT”,主要成分是NRS中的蛋白酶抑制剂,并开发了一系列化妆产品,可能销售不佳,近期已无法检索到相关产品,但仍不失为NRS高值化利用的一次积极探索。此外,鉴于EGT已具备一定的市场需求,从NRS中提取EGT也展现出较好的产业化应用潜力。
EGT是近年发展起来的新兴产业,其在我国的生产、应用历史不超过5年,但正处于快速发展阶段。EGT最初仅用于高端化妆品,2017年以来,随着批准其为新食品原料的国家增多,市场需求快速扩大。国内企业虽起步晚,但发展迅猛,2021年首次实现EGT的中试生产,到2024年,生产企业(含在建)已达约20家,全部投产后产能可达200 t以上。目前国内EGT生产全部采用生物合成法,而从NRS中提取EGT无需生物发酵,且NRS作为负成本原料,利用其生产EGT的成本远低于生物合成法,同时天然产物提取的安全性更高,因此在市场竞争中更具优势,市场前景广阔。
大量研究已经证实了NRS在生物医药领域的应用潜力,其中在促进伤口愈合和血管生成方面的活性机制研究最为深入。也有许多研究是将NRS的生物活性和天然胶乳结合起来[78],利用天然胶乳的生物相容性将天然胶乳作为药物递送的固体基质和药物释放系统,实现活性成分定期、更长时间和持续的药物释放[79]。目前,该方向因兼具理论创新性与技术可行性,有望成为NRS在生物医药领域的产业化应用中最具突破潜力的技术路径。
近年来,NR价格持续低迷,橡胶树种植效益和产业竞争力大幅下滑,植胶企业和农户的生产积极性受到严重打击,NR生产成本高、产业链短、产值低的弊端日益凸显,严重制约了产业的持续健康发展。而NRS的资源化利用,本质上是将NRS由废水属性向生产资料属性转变,将对废水的投入转变成向废水要产出,通过延长NR产业链,提升天然胶乳价值和生产效益,促进NR产业升级。因此,NRS的资源化利用不仅是环保需求的必然选择,更是产业升级的核心驱动力,具有广阔的发展前景。
  • 云南省科技厅农业基础研究联合专项(202301BD070001-068)
  • 云南省热带作物科技创新体系建设项目(RF2025)
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2025年第46卷第8期
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doi: 10.3969/j.issn.1000-2561.2025.08.019
  • 接收时间:2025-03-18
  • 首发时间:2026-06-24
  • 出版时间:2025-08-25
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  • 收稿日期:2025-03-18
  • 录用日期:2025-05-07
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云南省科技厅农业基础研究联合专项(202301BD070001-068)
云南省热带作物科技创新体系建设项目(RF2025)
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    云南省热带作物科学研究所/云南省天然橡胶可持续利用研究重点实验室(筹)/天然橡胶良种选育与栽培技术国家地方联合工程研究中心,云南景洪 666100

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* 张桂梅(ZHANG Guimei),E-mail:
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2种不同金属材料的力学参数

Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)

Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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