羧基修饰钯纳米粒子的DNA共轭物：制备与应用前景

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"该研究论文主要探讨了羧基修饰的钯纳米粒子(Pd NPs)在水溶液中的制备方法以及它们与DNA的共价结合。通过使用11-巯基十一烷酸(MUDA)作为稳定剂，成功制备出平均粒径为6纳米的Pd NPs，并研究了不同还原反应条件对纳米粒子形态的影响。利用多种技术如TEM、UV-Vis、FT-IR和XPS对制备的纳米粒子进行了详细表征。此外，DNA通过羧基活化共价键合到Pd NPs表面，这一过程通过琼脂糖凝胶电泳和荧光分析得到验证。所得的Pd NPs-DNA共轭物表现出对单碱基错配的高度识别能力，为Pd NPs在生物分析领域的应用奠定了基础。" 在本研究中，作者首次报道了一种新的策略来制备具有羧基功能化的钯纳米粒子。钯纳米粒子因其独特的化学性质和潜在的应用价值而备受关注，但其表面缺乏适合与生物分子如DNA结合的官能团。通过使用MUDA，一个含有硫醇基团的有机酸，研究人员能够在水性环境中稳定地合成Pd NPs。MUDA不仅提供了稳定的保护层，还通过硫醇基团与钯离子形成配位键，确保了纳米粒子的稳定性和尺寸控制。实验中，研究者系统地研究了不同还原条件对Pd NPs形态和尺寸的影响，这对于理解纳米粒子的生长机制和优化制备工艺至关重要。通过透射电子显微镜(TEM)可以观察到纳米粒子的形貌和大小，紫外线-可见光(UV-Vis)光谱则用于分析其光学特性，傅里叶变换红外光谱(FT-IR)揭示了纳米粒子表面的化学结构，而X射线光电子能谱(XPS)则提供了表面元素和化学状态的详细信息。接着，研究团队展示了如何通过羧基活化实现DNA与Pd NPs的共价连接，这是通过DNA的磷酸基团与Pd NPs表面的羧基进行反应实现的。这种结合方式的稳定性通过琼脂糖凝胶电泳进行验证，荧光分析进一步证明了DNA成功地连接到了纳米粒子上。实验结果表明，Pd NPs-DNA共轭物对于单碱基配对错误具有高度的识别敏感性，这表明它们可能在基因分析、DNA传感器或药物输送系统等领域具有潜在的应用价值。这项工作为钯纳米粒子在生物分析科学中的应用开辟了新的道路，尤其是通过改善其表面功能化，使得Pd NPs能够有效地与生物分子相互作用。这种羧基修饰的Pd NPs-DNA共轭物的开发，为未来研究提供了一个有前景的平台，有助于深入探索纳米材料在生物检测和诊断中的新角色。

Preparation of carboxyl group-modiﬁed palladium nanoparticles in an

aqueous solution and their conjugation with DNA

Zhifei Wang,

Hongying Li,

Shuang Zhen

and Nongyue He

Received 18th March 2012, Accepted 5th April 2012

DOI: 10.1039/c2nr30649b

The use of nanomaterials in biomolecular labeling and their corresponding detection has been

attracting much attention, recently. There are currently very few studies on palladium nanoparticles

(Pd NPs) due to their lack of appropriate surface functionalities for conjugation with DNA. In this

paper, we thus ﬁrstly present an approach to prepare carboxyl group-modiﬁed Pd NPs (with an average

size of 6 nm) by the use of 11-mercaptoundecanoic acid (MUDA) as a stabilizer in the aqueous solution.

The effect of the various reducing reaction conditions on the morphology of the Pd NPs was

investigated. The particles were further characterized by TEM, UV–vis, FT-IR and XPS techniques.

DNA was ﬁnally covalently conjugated to the surface of the Pd NPs through the activation of the

carboxyl group, which was conﬁrmed by agarose gel electrophoresis and ﬂuorescence analysis. The

resulting Pd NPs–DNA conjugates show high single base pair mismatch discrimination capabilities.

This work therefore sets a good foundation for further applications of Pd NPs in bio-analytical

research.

1. Introduction

The development of a variety of metal nanoparticle-based tech-

niques for DNA detection is an interesting alternative to the

standard ﬂuorescence technique due to their unique physico-

chemical properties, such as their large extinction and scattering

coefﬁcients, catalytic activity, surface electronics and efﬁcient

Brownian motion in solution.

1–5

For example, gold nanoparticles

(Au NPs) have been used extensively as biomolecular labels in

the past decades due to the ease of their synthesis and func-

tionalization, their limited toxicity and the ease of detection.

Consequently, no special requirements of the detection equip-

ment are required and the particles exhibit higher stability and

lower costs during bio-analysis applications.

6–10

However, in

contrast to the big advancement in Au NPs research, up to now,

there have been few reports on the applications of other noble

nanoparticles, such as Pd, in the biomedical ﬁeld. As a new kind

of functional material, Pd NPs have been developed in recent

years and have shown excellent performance in catalysis appli-

cations.

11–14

In DNA sensor applications, such properties can

also be used to substantially amplify the read-out signal through

the use of suitable reaction systems, such as electroless plating,

which present Pd NPs as an ideal potential label with a similar

behavior to the horseradish peroxidase (HRP) enzyme used in

enzyme-linked immunosorbent assays (ELISA).

15,16

One of the

reasons why Pd NPs have been poorly studied in biomolecular

detection is that Pd NPs with appropriate surface properties for

the conjugation of DNA are not currently available. Conse-

quently, the widely adopted Au NPs–oligonucleotide conjugate

chemistry,

such as ligand exchange reactions between thiol-

modiﬁed oligonucleotides and other pre-existing ligands on the

Au NPs’ surface, such as sodium citrate, can not be applied

for Pd NPs.

Up to now, many methods have been exploited for the

synthesis of Pd NPs with various shapes, sizes and surface

properties. These methods include wet and dry approaches, such

as gas-evaporation, the sol–gel method, hydrothermal

approaches and water-in-oil (w/o) microemulsions.

10–14,17–21

However, because the motivation for these syntheses have mainly

been driven by the catalytic applications of Pd NPs in organic

reactions, for example, to prevent the aggregation of Pd NPs in

organic solutions and/or to facilitate recycling of the catalyst,

such Pd NPs have been generally functionalized with a variety of

organic stabilizers, such as tetraoctylammonium bromide,

polyvinyl pyrrolidone (PVP),

dendrimers,

alkanethiols,

and

so on. Therefore, it has been difﬁcult to attach DNA to the

surfaces of PD NPs through simple ligand exchange reactions or

other strategies employed in biomolecular conjugation. Very

recently, Cargnello et al.

presented a versatile approach to

prepare functionalized thiol-protected Pd NPs. In their work,

they claimed that the obtained MUDA–Pd NPs had potential

applications in biology due to their high water solubility, which

was achieved through the conversion of surface carboxylic

groups to their carboxylate forms. However, this methodology

still remains complicated with regards to the post-synthesis

School of Chemistry and Chemical Engineering, Southeast University,

Nanjing 211189, China. E-mail: zfwang@seu.edu.cn; Fax: +86 (25)

83790885; Tel: +86 (25) 83790885

State Key Laboratory of Bioelectronics, Southeast University, Nanjing

210096, China

3536 | Nanoscale, 2012, 4, 3536–3542 This journal is ª The Royal Society of Chemistry 2012

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Cite this: Nanoscale, 2012, 4, 3536

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Published on 11 April 2012 on http://pubs.rsc.org | doi:10.1039/C2NR30649B

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