Simple synthesis of silver nanocluster composites AgNCs@PE-g-PAA by irradiation method and fluorescence detection of Cr^(3+)

Silver nanoclusters(AgNCs)are a new type of nanomaterials with similar properties to molecules and unique applications.The applications of AgNCs can be significantly expanded by combining them with different matrix materials to obtain AgNC composites.Using irradiation techniques,we developed a simple two-step method for preparing silver nanocluster composites.First,polyacrylic acid(PAA)chains were grafted onto the surface of a PE film as templates(PE-g-PAA).Subsequently,silver ions were reduced in situ on the surface of the template material to obtain the AgNC composites(AgNCs@PE-g-PAA).The degree of AgNC loading on the composite film was easily controlled by adjusting the reaction conditions.The loaded AgNCs were anchored to the carboxyl groups of the PAA and wrapped in the graft chain.The particle size of the AgNCs was only 4.38±0.85 nm,with a very uniform particle size distribution.The AgNCs@PE-g-PAA exhibited fluorescence characteristics derived from the AgNCs.The fluorescence of the AgNCs@PE-g-PAA was easily quenched by Cr^(3+)ions.The composite can be used as a fluorescence test paper to realize visual detection of Cr^(3+).

MOLECULAR DYNAMICS SIMULATION OF STRUCTURE STABILITY OF SILVER NANOCLUSTERS

The structures of Ag clusters with sizes n=13 to 1157 are studied by tight binding molecular dynamics simulation. It is found that the stable structures of Ag clusters follow the sequence amorphous-crystalline-amorphous-crystalline with the cluster size increasing from 13 to 1157. Furthermore, all the shells of Ag clusters are different from the structure of the corresponding bulk Ag.

Preparation of antibacterial non-woven AgNCs@PP-g-PAA via radiation method

With the growing threat of airborne epidemics,there has been an increasing emphasis on personal protection.Masks serve as our primary external defense against bacteria and viruses that might enter the respiratory tract.Hence,it’s crucial to develop a polypropylene(PP)nonwoven fabric with quick antibacterial capabilities as a key component for masks.This study introduces silver nanoclusters(AgNCs)into non-woven PP using radiation technology to infuse antibacterial properties.Initially,a solid ligand(PP-g-PAA)was procured via radiation grafting of the ligand polyacrylic acid(PAA),which was incorporated into the nonwoven PP with the aid of a crosslinking agent at a lower absorbed dosage.Subsequently,AgNCs were synthesized in situ on PP-g-PAA via an interaction between PAA and AgNCs,leading directly to the formation of AgNCs@PP-g-PAA composites.Owing to the hydrophilicity of PAA,AgNCs@PP-g-PAA maintains good moisture permeability even when the voids are heavily saturated with PAA gel,preventing droplet aggregation by diffusing droplets on the surface of the material.This feature enhances the comfort of the masks.Most importantly,due to the incorporation of AgNCs,AgNCs@PP-g-PAA demonstrates outstanding antibacterial effects against Escherichia coli and Staphylococcus aureus,nearly achieving an instant“touch and kill”outcome.In conclusion,we synthesized a modified nonwoven fabric with significant antibacterial activity using a simple synthetic route,offering a promising material that provides improved personal protection.

以卡托普利为模板银纳米团簇的制备及生物硫醇的检测研究

生物硫醇在生物体内的代谢过程中起着重要作用,如体内半胱氨酸(Cys)和谷胱甘肽(GSH)含量异常会引发一系列疾病。为了建立一种快速、定量检测生物硫醇的荧光分析方法,本文以卡托普利(Captopril,Capt)为模板,采用湿化学还原法成功合成了发红色荧光的银纳米团簇(Capt-Ag NCs),对Capt-Ag NCs的形貌、结构、元素组成和光学性能等进行了表征。基于生物硫醇小分子对Capt-Ag NCs的荧光猝灭作用建立了定量检测Cys和GSH的新方法,在最佳实验条件下,Cys和GSH的线性范围分别为1~100μmol/L和2~180μmol/L,检出限分别为0.054μmol/L和0.23μmol/L。该方法可用于人血浆中Cys的测定,回收率为95.3%~103.3%。实验结果表明,CaptAg NCs作为一种新型信号关闭荧光探针,可用于Cys和GSH等生物硫醇的检测。

荧光桃红B稳定剂制备银纳米簇及用于盐酸小檗碱的检测

本文以荧光桃红B为稳定剂,硝酸银为前驱体,硼氢化钠为还原剂,混合反应4 h制备得到具有荧光特性的银纳米簇(AgNCs)。实验显示,所合成的AgNCs的最佳激发波长为339 nm,最佳发射波长为444 nm。研究发现盐酸小檗碱(BH)能使合成的AgNCs的荧光显著猝灭,当BH浓度在1.25~12.50μmol/L范围内时,AgNCs的荧光强度的猝灭值(ΔI F)与BH浓度之间呈良好的线性关系,相关系数r为0.9958。基于此建立了一种测定BH的荧光分析方法,该方法的检出限为0.41μmol/L。同时,以紫外灯对体系进行照射时,pH浓度在3.75~12.50μmol/L范围时,溶液的颜色与pH浓度之间呈现梯度变化,因此可以建立一种更为简单的可视化检测BH的半定量检测方法。

基于银纳米簇比色传感器快速检测水果维生素C的方法

为提升水果品质分析效率,建立了基于银纳米簇比色传感器快速检测水果维生素C的方法。该方法以偏磷酸溶液萃取水果中的维生素C,以石墨化炭黑吸附干扰物质。以硝酸银水溶液和聚甲基丙烯酸钠水溶液混合加热搅拌4 h制备聚甲基丙烯酸修饰的银纳米簇材料,银纳米簇为球形,银纳米簇的平均直径为1 nm,加入维生素C以后,维生素C还原银离子从而增大了银纳米簇的尺寸并改变了银纳米簇溶液的光学性能,通过溶液颜色在感观上深浅变化和RGB色彩模式下蓝色值变化可实现维生素C含量的裸眼半定量分析和手机定量分析。在优化得到最佳检测条件后,结果表明,该检测方法可检出的维生素C最小含量为0.03 mg/kg,可定量的维生素C最小含量为0.1 mg/kg;该检测方法对葡萄糖、果糖、蔗糖、钙离子、锌离子、钾离子、叶酸等物质表现出了较好的抗干扰能力;该检测方法成功应用于橙、葡萄和梨果实维生素C的分析。将银纳米簇材料应用于水果的品质分析,有助于加快检测速度,降低检测成本,实现水果的精准快速分级。

沸石限域银纳米团簇发光材料的研究进展

沸石限域银纳米团簇具有制备方法简单、成本低、发光性能优异和稳定性好等优点,是一类具有广阔前景的新型发光材料,在发光二极管(Light emitting diode,LED)照明、防伪和传感等高新技术领域具有较高的应用价值,近来逐渐受到中外学者的广泛关注。本文总结了近年来沸石限域银纳米团簇的研究进展,重点讨论了这类发光材料的制备方法、发光性能调控以及它们在白光LED照明和小分子荧光检测方面的应用。此外,本文对该领域未来的发展进行了展望。

酪蛋白-金银合金纳米簇的制备及其对金霉素的荧光检测

以酪蛋白为保护剂和还原剂,采用优化的一锅加热合成方法,成功制备一种新型金银合金纳米簇(Au-AgNCs@casein)。产物在325 nm最佳激发波长下有双荧光发射峰,通过红外光谱、透射电子显微镜等方法对其进行结构表征。在常见离子或氨基酸存在下,金霉素(CTC)可明显增强比率型探针Au-AgNCs@casein的荧光,其结构类似物却无明显影响。因此,本研究中制备的纳米簇可快速、灵敏、选择性检测CTC。

基于HCR放大的无标记型荧光传感器的构建及H5N1 DNA检测

对于高致病性H5N1禽流感病毒,构建检测该病毒的高灵敏生物传感器,并与智能包装相结合用于实时监测,这对禽流感的防控具有重要意义。基于杂交链式反应(HCR)信号放大策略,以AgNCs作为荧光信号基团,构建了一种无标记“turn on”型荧光生物传感器用于检测代表H5N1病毒的H5N1基因序列。该传感器以H5N1 DNA作为触发剂引发HCR过程,使AgNCs产生强的荧光信号变化。研究表明,当H5N1 DNA浓度在0.2~800.0 nmol/L内,该传感器具有良好的响应信号,且在0.2~200.0 nmol/L之间的荧光强度与H5N1 DNA浓度呈线性相关,线性方程为y=10.982C+567.435(R^(2)=0.99273),检测限为176 pmol/L。核酸传感体系具有通用性,通过简单调整目标序列,可实现对不同目标物的特异性灵敏检测。该研究有望为高灵敏分析禽流感病毒标志物的通用传感平台设计提供思路。

Ag7(MBISA)6 Nanoclusters Conjugated with Quinacrine for FRET-Enhanced Photodynamic Activity under Visible Light Irradiation

Singlet oxygen(1 O2) plays an important role in various applications, such as in the photodynamic therapy(PDT) of cancers,photodynamic inactivation of microorganisms, photo-degradation of toxic compounds, and photo-oxidation in synthetic chemistry. Recently,water-soluble metal nanoclusters(NCs) have been utilized as photosensitizers for the generation of highly reactive 1 O2 because of their high water solubility, low toxicity, and surface functionalizability for targeted substances. In the case of metal NC-based photosensitizers, the photo-physical properties depend on the core size of the NCs and the core/ligand interfacial structures. A wide range of atomically precise gold NCs have been reported; however, reports on the synthesis of atomically precise silver NCs are limited due to the high reactivity and low photostability(i.e., easy oxidation) of Ag NCs. In addition, there have been few reports on what kinds of metal NCs can generate large amounts of 1 O2. In this study, we developed a new one-pot synthesis method of water-soluble Ag7(MBISA)6(MBISA= 2-mercapto-5-benzimidazolesulfonic acid sodium salt) NCs with highly efficient 1 O2 generation ability under the irradiation of white light emitting diodes(LEDs). The molecular formula and purity were determined by electrospray ionization mass spectrometry and gel electrophoresis. To the best of our knowledge, this is the first report on atomically precise thiolate silver clusters(Agn(SR)m) for efficient 1 O2 generation under visible light irradiation. The 1 O2 generation efficiency of Ag7(MBISA)6 NCs was higher than those of the following known water-soluble metal NCs: bovine serum albumin(BSA)-Au25 NCs,BSA-Ag8 NCs, BSA-Ag14 NCs,Ag25(dihydrolipoic acid)14 NCs,Ag35(glutathione)18 NCs,and Ag75(glutathione)40 NCs. The metal NCs examined in this study showed the following order of 1 O2 generation efficiency under white light irradiation: Ag7(MBISA)6 > BSA-Ag14 > Ag75(SG)40 > Ag35(SG)18 >BSA-Au25 >>BSA-Ags(not detected) and Ag2 s(DHLA)14(not detected). For further improving the 1 O2 generation of Ag7(MBISA)6 NCs, we developed a novel fluorescence resonance energy transfer(FRET) system by conjugating Ag7(MBISA)6 NCs with quinacrine(QC)(molar ratio of Ag NCs to QC is 1 : 0.5). We observed the FRET process,from QC to Ag7(MBISA)6 NCs,occurring in the conjugate. That is,the QC works as a donor chromophore,while the Ag NCs work as an acceptor chromophore in the FRET process. The FRET-mediated process caused a 2.3-fold increase in 1 O2 generation compared to that obtained with Ag7(MBISA)6 NCs alone. This study establishes a general and simple strategy for improving the PDT activity of metal NC-based photosensitizers.

Angle-sensitive and fast photovoltage of silver nanocluster embeded ZnO thin films induced by 1.064-μm pulsed laser

Silver nanocluster embedded ZnO composite thin film was observed to have an angle-sensitive and fast photovoltaic effect in the angle range from -90° to 90° , its peak value and the polarity varied regularly with the angle of incidence of the 1.064-μm pulsed Nd：YAG laser radiation onto the ZnO surface. Meanwhile, for each photovoltaic signal, its rising time reached -2 ns with an open-circuit photovoltage of -2 ns full width at half-maximum. This angle-sensitive fast photovoltaic effect is expected to put this composite film a candidate for angle-sensitive and fast photodetector.

一种基于银纳米簇免标记探针对ATP的检测

用三磷酸腺苷(Adenosine 3-triphosphate简称ATP)适配体BT5A5模板稳定的BT5A5-Ag Ncs探针检测ATP。当ATP出现时,ATP与适配体特异性结合诱导ATP适配体的构象发生改变,促使DNA两端荧光弱的Ag NCs相互靠近,导致荧光增强。测定了BT5A5-Ag NCs的TEM,BT5A5-Ag NCs的粒径均匀且在2 nm左右。在最佳条件下,ATP在0~15 mmo·L^(-1)性范围内的检测限为19μmol·L^(-1)。此方法成功地检测了胎牛血清中的ATP,回收率在98.3%~103.7%的范围。因此该方法对生物样品中ATP检测具有潜在的应用价值。

银纳米团簇复合材料的辐射法制备及性能研究

银纳米团簇作为一种新兴的纳米材料,由于其极小的尺寸,表现出独特的物理化学性能,得到了广泛的关注。本文利用辐射技术设计了一种简单有效的银纳米团簇复合材料的制备方法。利用聚丙烯酸类聚合物分子链携带的羧基,通过辐射还原直接获得了银纳米团簇水溶液。基于辐射接枝技术,将聚丙烯酸模板接枝到不同基体材料上得到固体模板。利用固体模板代替水溶性模板材料,实现了银纳米团簇在固体模板上的原位合成,直接得到银纳米团簇复合材料。制备的银纳米团簇及其复合材料依旧保有银纳米团簇光致发光及催化活性,在金属离子检测和催化4-硝基酚还原加氢具有应用潜力。同时,基体材料的结构与银纳米团簇也会形成协同作用,提高银纳米团簇的使用性能。利用辐射技术简化银纳米团簇复合材料的合成路线,对于不同基体材料具有普适性,扩宽了银纳米团簇复合材料的潜在应用领域。

DNA模板荧光金属纳米团簇的合成及应用

荧光金属纳米团簇的尺寸介于金属原子和纳米颗粒之间,特殊的结构和尺寸赋予了金属纳米团簇一系列优异的荧光特性,如荧光强度高、抗光漂白性能强、较大的斯托克斯位移。脱氧核糖核酸(DNA)由于其独特的结构和可设计的序列而成为合成金属纳米簇的理想模板。DNA模板的金属纳米簇主要包括DNA模板的银纳米团簇(DNA-AgNCs)、铜纳米团簇(DNA-CuNCs)、金纳米团簇(DNA-AuNCs)等。DNA模板的金属纳米团簇作为一种新型的荧光纳米探针在生物传感和生物成像等领域具有较大潜在应用价值。基于先前对DNA模板的金属纳米团簇的研究,系统总结了DNA模板的金属纳米簇的制备、性质和在生物传感以及生物成像中的应用。最后,讨论了DNA模板的金属纳米簇的未来发展研究重点和前景。

水溶性银纳米团簇的制备及其性能表征

本文以季戊四醇-四-3-巯基丙酸酯(PTMP)作为链转移剂,甲基丙烯酸(MAA)为单体,采用自由基聚合合成硫醚端基聚合物PTMP-PMAA。再以此聚合物作为配体,Ag NO3作为金属前驱体,在紫外光的辐照下合成了金属银纳米团簇(Ag NCs),并对制备的金属纳米团簇进行一系列合成优化以及表征。结果表明,所制备的Ag NCs的最佳激发波长为330 nm,最佳发射波长为625 nm,荧光量子效率为6.72%。

基于碳量子点-银纳米簇荧光共振能量转移纳米探针的荧光传感器检测转基因成分CaMV35S

利用荧光共振能量转移(FRET)纳米探针结合催化发夹组装(CHA)无酶扩增信号放大途径建立了一种可用于转基因成分的荧光检测方法。首先为CaMV35S目标序列(tDNA)设计了可诱导的CHA循环的两个发夹结构序列HP1和HP2。当单链DNA标记碳点(sDNA-CDs)和DNA模板化银纳米团簇(Ts-AgNCs)杂交后,AgNCs和碳量子点(CDs)靠近,形成FRET效应,得到sDNA-CDs/Ts-AgNCs荧光猝灭的比率荧光探针。当tDNA存在时,通过杂交反应打开HP1发夹,形成HP1-tDNA双链结构;该结构可将HP2的发夹结构打开,从而形成HP1-HP2双链结构,同时释放出tDNA进入下一轮杂交,触发CHA循环。由于HP1-HP2中HP1的部分序列与Ts部分序列间的亲和性较sDNA强,因此,加入sDNA-CDs/Ts-AgNCs后,sDNA-CDs从探针中释放,使CDs(λem=464 nm)的荧光得以增强。而AgNCs仍在双链结构中,其荧光强度(λem=560 nm)基本保持不变。以IF464/IF560为检测信号,在最优条件下,该比率荧光传感器对CaMV35S检测的线性范围为0.1~50 nmol/L,检出限(LOD,S/N=3)为0.02 nmol/L。制备的传感器具有良好的选择性,将该传感器用于转基因番茄叶中CaMV35S成分的检测,结果可靠。

脱氧核糖核酸-银纳米簇荧光探针用于沙眼衣原体的定量检测

采用化学法合成脱氧核糖核酸-银纳米簇(DNA-AgNCs)荧光探针,并用于沙眼衣原体色氨酸合成酶β链基因(目标序列)的选择性荧光检测。在pH 6.6乙酸盐缓冲溶液中加入两条DNA探针和硝酸银,在还原剂硼氢化钠作用下合成了荧光强度大的DNA-AgNCs。在pH 5.5乙酸铵缓冲溶液中加入目标序列和DNA-AgNCs溶液,使混合溶液体积达到100μL,其中DNA-AgNCs的浓度达到1.5μmol·L^(-1)(以DNA浓度计),于15℃反应10 min,目标序列与其中一条DNA探针杂交,DNA-AgNCs结构被破坏,检测体系荧光猝灭。结果显示:DNA-AgNCs颗粒呈类球形,粒径约为2 nm,分散性良好且未发生团聚,荧光激发、发射波长分别在558,610 nm处。猝灭程度ΔF(目标序列添加后、前的检测体系荧光强度的差值)与目标序列浓度在0.23~1.10μmol·L^(-1)内呈线性关系,检出限(3s/k)为57 nmol·L^(-1),测定值的相对标准偏差(n=11)为1.5%~4.9%。添加目标序列以及10倍目标序列浓度的同源序列、症状相似序列、衣原体序列和随机序列,仅目标序列加入时,检测体系荧光猝灭,说明合成的荧光探针具有优异的选择性;以海拉细胞裂解液和胎牛血清作模拟基质进行加标回收试验,回收率为98.0%~100%。

Host molecule enhanced aggregation induced emission of chiral silver nanoclusters for achieving highly efficient circularly polarized electroluminescence

Chiral metal nanoclusters(MNCs)are competitive candidates for fabricating circularly polarized light-emitting diodes(CPLEDs),but the device performance is greatly limited by the poor emission of MNCs in solid thin films.Herein,host molecule enhanced aggregation induced emission(AIE)of MNCs is demonstrated for fabricating highly efficient CPLEDs.Namely,on the basis of the AIE effect of atomically precise enantiomeric(R/S)-4-phenylthiazolidine-2-thione capped silver(R/S-Ag_(6)(PTLT)_(6))NCs in solid thin films,1,3-bis(carbazol-9-yl)benzene(mCP)is introduced as a host molecule to control the orientation and packing arrangements of R/S-Ag_(6)(PTLT)_(6) NCs throughπ–πinteractions with the R/S-Ag_(6)(PTLT)_(6) NCs and further enhance the AIE.The as-fabricated Ag_(6)(PTLT)_(6) NC/mCP hybrid solid thin film shows a high photoluminescence quantum yield of 71.0%close to that of Ag_(6)(PTLT)_(6) NC single crystal.As the hybrid films are employed as the active emission layers of CPLEDs,mCP also suppresses the triplettriplet annihilation and balances the charge transport.Thus,the CPLEDs exhibit a maximum brightness of 3,906 cd/m^(2),peak external quantum efficiency of 10.0%,electroluminescence dissymmetry factors of−5.3×10^(−3)and 4.7×10^(−3).

Alkynyl-anchored silver nanoclusters in lanthanide metal-organic framework for luminescent thermometer and CO_(2) cycloaddition

In this study,an alkynyl-modified aromatic dicarboxylic acid bifunctional ligand was selected to construct lanthanide compound{[Eu_(4)(ebdc)_(6)(4,4-bpy)_(0.5)(H_(2)O)_(4.5)]·(C_(2)H_(5)OH)_(1.25)(H_(2)O)}_(n)(Eu-MOF,H_(2)ebdc=5-ethynyl-isophthalic acid,4,4-bpy=4,4-bipyridine,MOF=metal-organic framework),of which the uncoordinated alkynyl group would be used to anchor silver nanoclusters(Ag NCs).The Eu-MOF exhibits double emission peaks,located at 492 and 611 nm,respectively,in which the high-energy blue emission is associated with alkynyl-modified ligand while the low-energy red emission belongs to characteristic emission of Eu3+,indicating that ligands can effectively sensitize Eu3+luminescence.The intensity ratio of the dual emission fluorescence peaks of Eu-MOF displays a good linear relationship with temperature,which realizes the detection function in the low temperature region of 75–275 K,the thermal sensitivity reaches 1.5398%·K^(−1).After anchoring the Ag NCs,the high-energy blue emission is significantly quenched,indicating that the Ag NCs are indeed confined into the framework and interact with the alkynyl group,and thus change the overall electronic distribution.This is the first case of anchoring Ag NCs by a luminescent Eu-MOF and studying nanocluster loading by using spectroscopic properties.In addition,the Ag NCs@Eu-MOF also shows a good catalytic activity for cycloaddition reaction from CO_(2)and epoxides.This study not only provides ideas for exploring the changes in optical properties of luminescent MOFs and Ag NCs caused by confinement effect,but also expands their potential applications in various fields.

金银合金发光纳米团簇研究进展

金银合金纳米团簇作为一类极具潜力的发光纳米复合材料,由于其结构精准、尺寸可控、光学性能可调谐、生物相容性良好等特性,在纳米生物医学前沿领域应用的研究具有重要意义,近年来也受到材料与化学科研工作者的广泛关注。本文主要回顾了金纳米团簇、银纳米团簇及金银合金纳米团簇的合成方法、结构设计及发光性质,综述了金银合金发光纳米团簇在生物成像、分子识别和光敏抗菌等生物医学方面的应用进展,并对其未来研究方向及应用前景进行了展望。