陳 嶸,榮凱峰,呂 中,曾琦斐，丘奕怡,梁惠強(qiáng),余響林

(1.武漢工程大學(xué)綠色化工過程省部共建教育部重點實驗室,湖北省新型反應(yīng)器與綠色化學(xué)工藝重點實驗室,湖北 武漢 430074;2.湖南環(huán)境生物職業(yè)技術(shù)學(xué)院，湖南 衡陽 421005；3.香港大學(xué)牙醫(yī)學(xué)院,香港)

0 引 言

隨著納米技術(shù)的迅猛發(fā)展,納米材料因其獨特的量子效應(yīng)、小尺寸效應(yīng)以及大的比表面積而顯現(xiàn)出特有的性質(zhì),引起人們廣泛的研究興趣.二十世紀(jì)九十年代以來,研究人員在納米材料的制備、表征上做了大量工作,取得了豐碩的研究成果.近年來,人們已越來越多的把目光集中在納米材料的性質(zhì)及其應(yīng)用上[1-2],而不是僅僅局限在材料的合成與制備.人類很早就認(rèn)識到了銀具有廣譜的抗菌作用,銀及其化合物,已廣泛應(yīng)用于日常生活和生物醫(yī)藥領(lǐng)域[3].而近年來,納米銀的研究更是取得了極為豐富的研究成果.在眾多的納米材料中,無論從制備、性質(zhì),還是應(yīng)用,納米銀無疑是一種研究最為廣泛、深入的材料.在已報道的文獻(xiàn)中,人們已經(jīng)通過不同的方法合成出不同粒徑和不同形貌的納米銀顆粒以及多種一維納米結(jié)構(gòu),如銀納米線、納米棒和具有一定空間結(jié)構(gòu)的樹枝狀的納米銀等.在納米銀的活性研究中,人們發(fā)現(xiàn)其不但具有顯著的抗菌活性[4-9],還具有抗病毒[10-11],抗腫瘤[12-13]等生物活性.正是這些顯著的生物活性,使得納米銀在生物醫(yī)藥和紡織上得到廣泛的應(yīng)用[14],并且已有多種關(guān)于納米銀的產(chǎn)品市場化.本文簡要綜述了不同粒徑和形貌的納米銀的各種制備方法,及其抗菌、抗病毒、抗腫瘤等生物活性和其產(chǎn)業(yè)化應(yīng)用.

1 納米銀的制備

在不同形貌和大小的銀納米結(jié)構(gòu)的制備方法中,根據(jù)所用還原劑或還原方法的不同,主要分為三類:化學(xué)還原法、物理還原法、生物還原法.

1.1 化學(xué)還原法

化學(xué)還原法是制備納米銀最簡單也最常用的方法.一般指在液相條件下,將Ag+還原為單質(zhì)銀,所用還原劑常有硼氫化鈉、檸檬酸鈉、乙二醇、抗壞血酸、葡萄糖等.不同的還原劑和分散劑對納米銀的形貌和大小有很大的影響,在納米銀顆粒的合成中,人們通過控制不同的反應(yīng)條件,分別得到了不同粒徑大小的納米銀顆粒(如圖1所示).例如,Logar等以NaBH4為還原劑,制備得到顆粒大小為7 nm左右的納米銀顆粒[15].Lee課題組報道了利用1,2-二羥基十六烷還原Ag+得到晶種并通過銀納米粒子的自組裝,得到粒徑為10 nm左右的單分散納米銀顆粒[16].殷亞東課題組還報道了使用多羥基還原的方法,以乙二醇為溶劑和還原劑,并且使用聚丙烯酸(PAA)為表面活性劑,得到了粒徑為20 nm的銀納米顆粒[17].夏幼南課題組在引入少量NaCl的條件下,以乙二醇為溶劑和還原劑,可得到粒徑為30 nm左右的銀納米顆粒及其二聚體[18].還有報道直接用檸檬酸鈉還原硝酸銀,可制備出了30～50 nm的銀納米顆粒[19]. 陳代榮課題組使用抗壞血酸還原氯化銀可得到50 nm的銀納米顆粒[20].Pyatenko等采用晶種技術(shù),首先生成納米銀種子顆粒,然后合成納米銀溶膠,再經(jīng)多步合成過程,便可得到80 nm左右的納米銀顆粒[21].Quaroni等使用乳液聚合作用,制備了尺寸均一、穩(wěn)定、粒徑為100 nm的納米銀顆粒[22].

圖1 不同粒徑的納米銀顆粒透射電鏡圖

目前,除了用各種方法制備出不同粒徑的銀納米顆粒外,人們也制備出了銀納米線[23-25]、納米立方[26-27]、納米棒[28-29]、納米球[30]、納米三角片[31]、納米雙錐體[32]等不同形貌結(jié)構(gòu)(如圖2所示).

圖2 不同形貌的納米銀掃描電鏡圖

夏幼南課題組報道在PVP存在下,用乙二醇還原AgNO3,以Pt或Ag的小粒徑的納米顆粒作為晶種,合成出長度50 μm,直徑30～40 nm的銀納米線[23-24].夏幼南課題組還報道了使用多羥基還原的方法,在PVP存在條件下,通過改變PVP與AgNO3的摩爾比,可控合成了平均粒徑為80±7 nm的銀納米立方結(jié)構(gòu)[26].該課題組還使用多羥基還原的方法,通過控制納米銀種子晶型來控制最終產(chǎn)物的形貌,選擇性的合成出不同形狀的銀納米結(jié)構(gòu),如納米三角、納米雙錐體、納米棒、納米線、納米束、納米立方體、納米球等結(jié)構(gòu),并通過調(diào)節(jié)AgNO3濃度,PVP與AgNO3的比例等因素也可來改變納米銀的粒徑和形貌[31-33].在此基礎(chǔ)上,Yam課題組使用水熱法,以葡萄糖為還原劑還原[Ag(NH3)2]+得到邊長為55±5 nm的銀納米立方結(jié)構(gòu)[27].錢逸泰課題組使用水熱法,并以氯化銀作為前驅(qū)體反應(yīng)生成銀的納米線,其長度可達(dá)500 μm,平均直徑約為100 nm[25].Maiyalagan利用多元醇方法通過改變AgNO3與PVP的比例,得到不同長徑比的銀納米棒[28].Pietrobon等采用水熱法,并以檸檬酸為還原劑,將單分散的納米銀顆粒,自組裝成銀的納米棒結(jié)構(gòu)[29].Liang等采用水熱法,使用聚乙二醇(PEG)作為還原劑和溶劑,通過控制PVP與AgNO3的摩爾比,制備出了單分散的銀納米球結(jié)構(gòu)[30].李亞棟課題組通過溶劑熱法,合成三角片、球型、立方體形狀的納米銀[34].化學(xué)還原法操作簡單,容易控制,常使用表面活性劑(如PVP、CTAB、PEG、SDS等)防止納米銀顆粒聚集,并誘導(dǎo)其晶體生長.

1.2 物理還原法

物理還原法主要是指借助于物理手段或方法等輔助條件將Ag+還原為單質(zhì)銀的方法,主要有:紫外光照射法、電子束輻射法、微波還原法等.Giovanna等使用紫外光照射的方法制備出2～4 nm的納米銀顆粒[35].在聚乙烯醇(PVA)存在下,通過電子束輻射,可將AgNO3還原制得穩(wěn)定的銀納米粒子[36-37].而微波法由于具有加熱速度快、加熱均勻、無溫度梯度、無滯后效應(yīng)等特點,近年來也被廣泛應(yīng)用于納米銀顆粒的制備.在乙二醇溶劑里,通過微波加熱可制備得到粒徑為10 nm左右的納米銀顆粒[38].俞書宏課題組發(fā)現(xiàn)在AgNO3中加入一定比例的氨基酸、淀粉,通過微波加熱也可合成出平均粒徑約為26 nm的納米銀顆粒[39].Baruwati等人還報道了在谷胱甘肽促進(jìn)下,水溶液中微波合成粒徑為5～10 nm的納米銀顆粒[40].

1.3 生物還原法

隨著人們對環(huán)境友好型技術(shù)的逐漸重視,研究人員發(fā)現(xiàn)利用微生物體系也可來制備納米銀顆粒.生物還原法主要有:細(xì)菌還原法、真菌還原法、植物還原法等[3].1999年,Klaus等首次報道了利用施氏假單胞菌合成銀的納米顆粒,高濃度AgNO3在施氏假單胞菌中被還原成顆粒大小為200 nm左右的銀納米晶體[41](如圖3所示).隨后不同研究小組分別報道了用肺炎克雷伯桿菌[42]、地衣芽孢桿菌[43-44]、煙曲霉菌[45]、黃曲霉[46]、黑曲霉[47]、木霉菌[48]、白腐真菌[49]、尖孢鐮刀菌[50]等與Ag+作用得到不同粒徑的納米銀顆粒.除細(xì)菌、真菌外,印度學(xué)者還報道了用植物還原法合成納米銀.研究發(fā)現(xiàn)天竺葵葉提取物在較短時間內(nèi),可將銀離子還原成粒徑為16～40 nm的銀納米顆粒[51].李清彪課題組也報道了利用香樟葉合成粒徑約為55～80 nm的銀納米顆粒[52].生物還原法具有原料來源廣、價廉易得、綠色環(huán)保、反應(yīng)條件溫和等優(yōu)點,可能引領(lǐng)一種簡易的生物合成納米銀方法的新發(fā)展,但其還原能力較弱,尋找新的具有較強(qiáng)還原能力的生物源是此法的主要突破口.

圖3 施氏假單胞菌細(xì)胞的超薄切片的高分辨透射電子顯微鏡照片

2 納米銀的生物活性

2.1 納米銀的抗菌活性

人類很早就認(rèn)識到銀具有廣譜殺菌作用,并用銀來殺菌消毒.近年來,隨著納米技術(shù)的發(fā)展,納米級無機(jī)抗菌劑的應(yīng)用日益廣泛.其中納米銀系列抗菌劑是研究最為廣泛和深入的納米抗菌材料,有關(guān)納米銀的抗菌活性的報道層出不窮,研究發(fā)現(xiàn),納米銀對大腸桿菌、金黃色葡萄球菌有較好的抑制作用[6-7,53-60],不同研究小組還分別報道了納米銀對枯草芽孢桿菌[8,61]、銅綠假單胞菌[62-63],鼠傷寒少門氏桿菌[64]、真菌[65]等的抗菌作用.隨后Hernández-Sierra等報道了其對口腔細(xì)菌:致齲菌變形鏈球菌的抑制作用[9,66].Arora等研究了納米銀顆粒經(jīng)細(xì)胞毒性實驗、動物實驗,證明納米銀基本屬無生物毒性的納米材料,其具有高效抗菌活性并且使用安全[67-68].支志明課題組系統(tǒng)研究了納米銀對大腸桿菌的抑制作用,并探討了其抗菌機(jī)制,說明納米銀可能是通過破壞細(xì)菌細(xì)胞膜,從而消耗其質(zhì)子驅(qū)動力,這樣來達(dá)到其抗菌效果[69-71].Sondi等在前人研究的基礎(chǔ)上總結(jié)了銀系抗菌劑的抗菌機(jī)理,他們指出納米銀顆?？梢灾苯舆M(jìn)入微生物體內(nèi),中斷DNA的復(fù)制,通過阻斷細(xì)菌的呼吸酶系統(tǒng),殺滅細(xì)菌,從而阻止微生物繁殖,殺滅各種致病細(xì)菌[7,72].

2.2 納米銀的抗病毒活性

人們對銀的抗病毒活性研究起步較晚,隨著納米科技的快速發(fā)展,近年,人們對納米銀的抗病毒活性研究越來越多.2005年,Yacaman課題組和支志明課題組相繼報道了納米銀對HIV病毒的抑制作用,研究表明粒徑在1～30 nm的納米銀顆粒均能起到殺滅HIV病毒的作用,阻止其HIV病毒的繁殖[10,73].2008年,支志明課題組和Rogers課題組又相繼報道了納米銀對乙型肝炎病毒[11]和腥紅熱病毒[74]的抑制作用.張若愚等人還報道了納米銀顆粒對禽流感病毒也有較好的抑制作用[75].

2.3 納米銀的抗腫瘤活性

盡管納米銀在抗腫瘤活性方面的研究不及抗菌活性方面的研究廣泛,但也有不少研究小組對其抗腫瘤活性做了相關(guān)報道.Gopinath 等報道了納米銀可以使細(xì)胞內(nèi)線粒體膜通透性發(fā)生改變,從而促進(jìn)腫瘤細(xì)胞凋亡[76].Verma等也研究了納米銀具有較好的抗癌活性[77].Otrock等報道了納米銀的靶向治療,在殺死癌細(xì)胞時,對正常細(xì)胞沒有損傷[78].Youngs等報道了納米銀對乳腺癌細(xì)胞的抑殺作用[12].在預(yù)防和治療與細(xì)胞凋亡缺陷有關(guān)的疾病方面(如惡性腫瘤等),納米銀的作用值得進(jìn)一步深入研究.

3 納米銀產(chǎn)品

由于納米銀具有廣譜抗菌性,且其有抗菌活性高、毒性低等特點,載銀納米無機(jī)抗菌材已成為目前應(yīng)用最廣泛的無機(jī)抗菌材料.國內(nèi)外研究人員研制出的相應(yīng)的納米銀產(chǎn)品已應(yīng)用于各領(lǐng)域.例如:香港安信納米科技公司率先研發(fā)的納米銀速效抗菌顆粒,已通過香港大學(xué)、中國科學(xué)院、中國醫(yī)學(xué)院等權(quán)威機(jī)構(gòu)的認(rèn)證并投產(chǎn).除此以外,安信公司還研制開發(fā)了納米抗菌襪、納米銀創(chuàng)可貼等納米產(chǎn)品.江蘇瑞德納米材料技術(shù)有限公司推出的宣氏納米銀抗菌凝膠(燒傷用),其產(chǎn)品具有超強(qiáng)的抗菌活性,能促進(jìn)組織修復(fù)與再生,加快創(chuàng)面愈合,減少疤痕組織的形成.中山市國宇醫(yī)療器械有限公司開發(fā)研制的納米銀痔瘡凈、沈陽高名醫(yī)藥科技有限公司的納米銀前列寶、濟(jì)南龍邦生物科技有限公司的納米銀腳癬凈、西安華康生物科技有限公司婦科千金(納米銀)凝膠、上海滬正納米科技有限公司的納米銀牙膏以及深圳清華源興納米醫(yī)藥科技有限公司研制開發(fā)的納米銀制劑阿希米都已經(jīng)產(chǎn)業(yè)化.

4 總結(jié)與展望

隨著納米科技的發(fā)展,納米銀在人類生活中有著舉足輕重的作用.近年來通過化學(xué)還原法和物理還原法可以合成出不同大小、不同形貌的納米銀.以細(xì)菌、真菌以及植物為原料的生物還原法也是具有很大的潛力的綠色合成方法.未來的納米銀制備方法將向低成本、低能耗、環(huán)境友好的方向發(fā)展.納米銀對常見革蘭氏陰性菌和革蘭氏陽性菌都有較好的抗菌作用,其抗菌活性高、抗菌譜廣且毒性較低等,其且對HIV病毒、腥紅熱病毒及禽流感病毒均有較好的抑制作用.納米銀還可通過靶向治療促使腫瘤細(xì)胞凋亡.隨著人們對其抗菌、抗病毒、抗腫瘤原理及其活性與生物穩(wěn)定性研究的進(jìn)一步深入,將開發(fā)出更多安全、有效的納米銀制劑.由于納米銀在生物醫(yī)學(xué)等方面有著廣泛的應(yīng)用,其產(chǎn)業(yè)化引起了人們的高度重視,并且許多成果已經(jīng)開始產(chǎn)業(yè)化.真正全面實現(xiàn)納米銀的產(chǎn)業(yè)化,造福人類,也是當(dāng)前科技工作者努力的方向.

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