壳聚糖及其在金属纳米材料制备中的应用

基于来源丰富、独特的理化性质及生物学特性的壳聚糖与金属复合成为纳米材料的研究,引起了研究者广泛的关注。人们利用生物分子或生物有机体合成的金属纳米材料反应条件温和、产物形貌可控、重复性高等特点,结合金属纳米材料的"尺寸效应"与生物分子的自身特性来提高两者的协同功能,进一步拓展研究与应用领域的发展。以下针对近年来壳聚糖、壳聚糖体系金属纳米材料的研制及应用等领域进行简要的总结、评述和展望。     

合成生物学在生物材料科学中的应用及展望

生物材料的发展最早以生物惰性的工业材料为主,而后过渡到具有生物活性的材料,再发展为具备与生物体有可控生物反应的材料。未来,随着老龄化时代的来临以及精准医学的需求,生物材料的发展必然朝着动态可调控、高效多功能及仿生交互的方向发展。合成生物学以基因回路设计为核心,采用标准化元件在人造生物器件中实现可控的复杂功能,极大地推动了生命科学的发展。简要回顾了生物材料的发展,重点介绍了合成生物学在组织工程支架、可控药物输送体系、生物杂化材料及工程活体材料方面的应用,并讨论了未来合成生物学将如何更深远地影响生物材料的发展以及合成生物学在生物材料应用方面需要克服的一些挑战。     

DNA-金属纳米材料在分子识别和药物递送中的应用

分子识别和药物递送对疾病的早期诊断和靶向治疗至关重要。DNA作为一种天然纳米分子，具有良好的生物相容性、分子识别性及序列可编程性等特点，因此在生物医学研究中受到广泛关注。然而，DNA纳米材料存在依赖于光响应系统且不能穿透细胞膜等缺点，导致单独使用无法满足实际应用的需求。近年来，涌现出大量DNA-金属纳米材料，这些复合材料具有光化学特性、组织穿透能力和药物装载能力等功能，克服了单一材料的缺陷，在生物传感、生物成像和药物靶向递送中表现出巨大的应用潜力。本文集中于3种近年热门的DNA-金属纳米材料（DNA-铜纳米材料、DNA-上转换纳米材料、DNA-金属有机框架纳米材料），依据DNA与各金属纳米材料的结合方式进行合理分类，介绍其在生物传感、生物成像和药物递送中的最新应用进展，并对未来发展方向进行了展望。     

磷烯纳米材料的生物毒性研究进展

磷烯,即单层黑磷（BP）,由于具有直接带隙、显著的结构和功能各向异性、高电荷载流子迁移率等,已经在生物医学、药物输送、生物传感、疾病的诊断和治疗等领域取得了很大的进展。和其他纳米材料相比,磷烯具有更优异的生物相容性和生物可降解性,在生物医药领域有很好的应用前景。虽然已有大量磷烯生物学效应的报道,但磷烯与生物大分子,如核酸、脂质、蛋白质之间相互作用的过程细节仍缺乏系统的研究。目前实验上无法观测磷烯与生物分子相互作用的动力学过程,分子模拟在获取精确动态结构方面具有独特的优势,被广泛应用于纳米材料和生物学领域。本文综述了近年来国内外利用计算机仿真和实验方法在磷烯纳米材料与蛋白质、脂质膜和DNA等生物大分子相互作用方面取得的最新研究进展,对磷烯生物毒性目前的研究进行了评述,并对未来需要解决的问题作了分析。本文将促进磷烯生物学效应的基础研究,也将推动磷烯纳米材料在生物医药领域的应用。     

纳米材料生物效应研究进展

随着纳米技术的快速发展,纳米材料在医学成像、疾病诊断、药物传输、癌症治疗、基因治疗等领域的应用和基础研究也在飞速发展.同时,纳米材料的这些有益应用使得人体通过吸入、经口、皮肤吸收和静脉注射等不同方式受到暴露.当纳米材料与生物体系发生相互作用时,有可能产生负面生物学效应,而这些潜在的毒理效应都是未知的.综述了纳米材料在生物医学领域巨大的应用前景,关注其对心血管系统、呼吸系统及转运到其他器官可能造成的负面效应,并探讨了纳米颗粒在引起心血管疾病及肺部炎症方面的可能机理与作用途径.最后对纳米材料的安全性评估和研究重点进行了总结.     

医用金属及金属氧化物纳米材料的毒性研究

随着纳米科技的发展,纳米材料在各领域的应用日益增多。金属及金属氧化物纳米材料因其独特的物化性质,为多种疾病的诊治提供了崭新的解决途径。其中,贵金属金、银及应用最为广泛的铁所形成的纳米材料在医学领域应用甚广。纳米金及纳米银具有优异的抗菌效能,广泛用于伤口敷料、化妆品、食品等的制造中。除此之外,纳米金、纳米银及含铁的磁性纳米颗粒也用于疾病诊治方面,如肿瘤的诊断和治疗、生物传感器、生物成像等。但是,大部分金属纳米材料可对机体产生不良作用,因而了解金属纳米材料的毒性显得非常重要。为了在医学应用中更有效地利用金属纳米材料,必须探究其大小、表面化学、特殊性质及毒性。本文总结了这几种金属纳米材料的医学用途,概述了它们的体内外毒性,并分析了可能的毒性作用机制。     

纳米生物学的研究现状与关键科学问题

作为一门交叉学科,纳米生物学成为当前生命科学研究在纳米尺度上的前沿与热点.本文从文献计量学的视角,分析了近年来纳米生物学领域的论文发表数量和被引用情况,重点关注了纳米生物医学、纳米生物材料、纳米生物化学和纳米生物物理4个主要分支领域的基本情况和研究主题,呈现了纳米生物学可视化的知识图谱;并结合战略研讨和专家研判,凝练获得了纳米生物学6个方面的关键科学问题,以期为纳米生物学未来的研究思路提供参考.     

介孔碳纳米材料的制备及其在药物传递方面的应用进展

新型功能性纳米材料在设计和制备技术方面的进步为纳米医学的发展提供了很大的机遇。在过去十年中,介孔碳纳米材料在制备和应用方面获得了巨大的进步。作为一种新型无机材料体系,介孔碳纳米材料结合了介孔的结构以及碳质组成的特点,显示出不同于传统介孔二氧化硅以及其它一些碳基材料体系(碳纳米管、石墨烯、富勒烯等)的优越特性。介孔碳纳米材料在药物的吸附与控释、光热治疗、协同治疗、肿瘤细胞的荧光标记、催化、生物传感、生物大分子的分离等诸多领域表现出其他多孔材料难以达到的优越性和应用潜力。本文对介孔碳纳米材料的制备和修饰技术进行介绍,重点关注介孔碳纳米颗粒在药物负载和光热控释方面的应用,最后对介孔碳纳米材料在生物医学领域的应用前景和所面临的关键问题进行讨论。     

硫化铜纳米粒子应用于肿瘤诊断和治疗的研究进展

癌症是当今威胁人类健康的主要疾病之一。近年来提出的近红外光介导的光热治疗,能够对肿瘤组织进行定点清除并且对正常组织具有较低的毒副作用,为肿瘤的治疗提供了新的方法。开发具有良好生物相容性的高效光热偶联剂是发展光热治疗的首要条件。随着纳米技术的飞速发展,一些金属纳米结构由于具有独特的光学特性作为光热偶联剂被广泛应用到肿瘤的光热治疗中。然而,成本高昂、制备过程繁琐以及光热稳定性较差等不足,限制了这些纳米材料的进一步应用。最新报道的新型光热偶联剂半导体硫化铜纳米粒子(copper sulfide nanoparticles,CuS NPs),由于其具有制备工艺简单、成本低廉、突出的光热稳定性和良好的生物相容性等优势,成为了当今纳米医学领域研究的热点。本文主要综述了CuS纳米粒子在肿瘤光热治疗和影像诊断方面的应用研究,并对CuS纳米粒子在生物医学领域应用中存在的问题和未来的研究方向进行了展望。     

融合酶构建技术在酶的改性以及多功能酶的构建方面的应用

融合酶技术是酶的改造技术之一。应用融合酶技术还可以创造出多功能的新酶,这些新酶有望应用于食品、化工等领域。目前研究表明,融合酶在低聚糖制备,生物燃料,生物材料,氨基酸发酵以及生物传感器等领域极具应用前景。融合酶的构建技术有理性设计和非理性设计,这两种技术各有利弊。整理了近年融合酶在以上领域中的研究成果,对融合酶的工业应用进行讨论。     

Peptide-conjugated gold nanorods for nuclear targeting

Resonant electron oscillations on the surface of noble metal nanoparticles (Au, Ag, Cu) create the surface plasmon resonance (SPR) that greatly enhances the absorption and Rayleigh (Mie) scattering of light by these particles. By adjusting the size and shape of the particles from spheres to rods, the SPR absorption and scattering can be tuned from the visible to the near-infrared region (NIR) where biologic tissues are relatively transparent. Further, gold nanorods greatly enhance surface Raman scattering of adsorbed molecules. These unique properties make gold nanorods especially attractive as optical sensors for biological and medical applications. In the present work, gold nanorods are covalently conjugated with a nuclear localization signal peptide through a thioalkyl-triazole linker and incubated with an immortalized benign epithelial cell line and an oral cancer cell line. Dark field light SPR scattering images demonstrate that nanorods are located in both the cytoplasm and nucleus of both cell lines. Single cell micro-Raman spectra reveal enhanced Raman bands of the peptide as well as molecules in the cytoplasm and the nucleus. Further, the Raman spectra reveal a difference between benign and cancer cell lines. This work represents an important step toward both imaging and Raman-based intracellular biosensing with covalently linked ligand-nanorod probes.     

Plasmonic Optical Properties and Applications of Metal Nanostructures

In this review article, we provide an overview of recent research activities in the study of plasmonic optical properties of metal nanostructures with emphasis on understanding the relation between surface plasmon absorption and structure. Both experimental results and theoretical calculations have indicated that the plasmonic absorption strongly depends on the detailed structure of the nanomaterials. Examples discussed include spherical nanoparticles, nanorods, nanowires, hollow nanospheres, aggregates, and nanocages. Plasmon–phonon coupling measured from dynamic studies as a function of particle size, shape, and aggregation state is also reviewed. The fascinating optical properties of metal nanostructures find important applications in a number of technological areas including surface plasmon resonance, surface-enhanced Raman scattering, and photothermal imaging and therapy. Their novel optical properties and emerging applications are illustrated using specific examples from recent literature. The case of hollow nanosphere structures is highlighted to illustrate their unique features and advantages for some of these applications.     

Plasmonic, Low-Frequency Raman, and Nonlinear Optical-Limiting Studies in Copper–Silica Nanocomposites

Nanocomposite thin films consisting of Cu nanoparticles embedded in silica matrix were synthesized by atom beam co-sputtering technique. Plasmonic, optical, and structural properties of the nanocomposite films were investigated by using ultraviolet (UV)–visible absorption spectroscopy, nonlinear optical transmission, X-ray diffraction (XRD), and low-frequency Raman scattering. UV–visible absorption studies revealed the surface plasmon resonance absorption at 564 nm which showed a red shift with increase in Cu fraction. XRD results together with surface plasmon resonance absorption confirmed the presence of Cu nanoparticles of different size. Low-frequency Raman studies of nanocomposite films revealed breathing modes in Cu nanoparticles. Nanocomposites with lower metal fractions were found to behave like optical limiters. The possibility of controllably tuning the optical nonlinearity of these nanocomposites could enable them to be the potential candidates for applications in nanophotonics.     

DNA‐Functionalized Plasmonic Nanomaterials for Optical Biosensing

Plasmonic nanomaterials, especially Au and Ag nanomaterials, have shown attractive physicochemical properties, such as easy functionalization and tunable optical bands. The development of this active subfield paves the way to the fascinating biosensing platforms. In recent years, plasmonic nanomaterials–based sensors have been extensively investigated because they are useful for genetic diseases, biological processes, devices, and cell imaging. In this account, a brief introduction of the development of optical biosensors based on DNA‐functionalized plasmonic nanomaterials is presented. Then the common strategies for the application of the optical sensors are summarized, including colorimetry, fluorescence, localized surface plasmon resonance, and surface‐enhanced resonance scattering detection. The focus is on the fundamental aspect of detection methods, and then a few examples of each method are highlighted. Finally, the opportunities and challenges for the plasmonic nanomaterials–based biosensing are discussed with the development of modern technologies.     

Mapping the Progress in Surface Plasmon Resonance Analysis of Phytogenic Silver Nanoparticles with Colorimetric Sensing Applications

Nanotechnology is gaining enormous attention as the most dynamic research area in science and technology. It involves the synthesis and applications of nanomaterials in diverse fields including medical, agriculture, textiles, food technology, cosmetics, aerospace, electronics, etc. Silver nanoparticles (AgNPs) have been extensively used in such applications due to their excellent physicochemical, antibacterial, and biological properties. The use of plant extract as a biological reactor is one of the most promising solutions for the synthesis of AgNPs because this process overcomes the drawbacks of physical and chemical methods. This review article summarizes the plant-mediated synthesis process, the probable reaction mechanism, and the colorimetric sensing applications of AgNPs. Plant-mediated synthesis parameters largely affect the surface plasmon resonance (SPR) characteristic due to the changes in the size and shape of AgNPs. These changes in the size and shape of plant-mediated AgNPs are elaborately discussed here by analyzing the surface plasmon resonance characteristics. Furthermore, this article also highlights the promising applications of plant-mediated AgNPs in sensing applications regarding the detection of mercury, hydrogen peroxide, lead, and glucose. Finally, it describes the future perspective of plant-mediated AgNPs for the development of green chemistry.     

Bare laser‐synthesized Au‐based nanoparticles as nondisturbing surface‐enhanced Raman scattering probes for bacteria identification

The ability of noble metal‐based nanoparticles (NPs) (Au, Ag) to drastically enhance Raman scattering from molecules placed near metal surface, termed as surface‐enhanced Raman scattering (SERS), is widely used for identification of trace amounts of biological materials in biomedical, food safety and security applications. However, conventional NPs synthesized by colloidal chemistry are typically contaminated by nonbiocompatible by‐products (surfactants, anions), which can have negative impacts on many live objects under examination (cells, bacteria) and thus decrease the precision of bioidentification. In this article, we explore novel ultrapure laser‐synthesized Au‐based nanomaterials, including Au NPs and AuSi hybrid nanostructures, as mobile SERS probes in tasks of bacteria detection. We show that these Au‐based nanomaterials can efficiently enhance Raman signals from model R6G molecules, while the enhancement factor depends on the content of Au in NP composition. Profiting from the observed enhancement and purity of laser‐synthesized nanomaterials, we demonstrate successful identification of 2 types of bacteria (Listeria innocua and Escherichia coli). The obtained results promise less disturbing studies of biological systems based on good biocompatibility of contamination‐free laser‐synthesized nanomaterials.

     

Tunable Absorption of Light via Localized Plasmon Resonances on a Metal Surface with Interspaced Ultra-thin Metal Gratings

We studied optical reflection properties of complex metal (Ag) surfaces with close-interspaced ultra-thin metal gratings. Prominent reflection minima were observed corresponding to enhanced absorption of light. Our analysis convinced us that the period-dependent mode is ascribed to Bloch-wave-like resonances of surface plasmon waves at the overall effective metal surfaces, and the ridge-width-dependent mode to Fabry-Pérot-like resonances of localized surface plasmon waves in micro-/nanocavities defined by regions of the grating ridges. The latter resonance mode is shown highly tunable with variation of the grating ridge width. Such structures may be applied in spectrum resolvable photovoltaic devices, bio-sensing, and studying optical properties of cavity-coupled molecules or functional nanomaterials.     

Radiative decay engineering 5: metal-enhanced fluorescence and plasmon emission

Metallic particles and surfaces display diverse and complex optical properties. Examples include the intense colors of noble metal colloids, surface plasmon resonance absorption by thin metal films, and quenching of excited fluorophores near the metal surfaces. Recently, the interactions of fluorophores with metallic particles and surfaces (metals) have been used to obtain increased fluorescence intensities, to develop assays based on fluorescence quenching by gold colloids, and to obtain directional radiation from fluorophores near thin metal films. For metal-enhanced fluorescence it is difficult to predict whether a particular metal structure, such as a colloid, fractal, or continuous surface, will quench or enhance fluorescence. In the present report we suggest how the effects of metals on fluorescence can be explained using a simple concept, based on radiating plasmons (RPs). The underlying physics may be complex but the concept is simple to understand. According to the RP model, the emission or quenching of a fluorophore near the metal can be predicted from the optical properties of the metal structures as calculated from electrodynamics, Mie theory, and/or Maxwell's equations. For example, according to Mie theory and the size and shape of the particle, the extinction of metal colloids can be due to either absorption or scattering. Incident energy is dissipated by absorption. Far-field radiation is created by scattering. Based on our model small colloids are expected to quench fluorescence because absorption is dominant over scattering. Larger colloids are expected to enhance fluorescence because the scattering component is dominant over absorption. The ability of a metal's surface to absorb or reflect light is due to wavenumber matching requirements at the metal-sample interface. Wavenumber matching considerations can also be used to predict whether fluorophores at a given distance from a continuous planar surface will be emitted or quenched. These considerations suggest that the so called "lossy surface waves" which quench fluorescence are due to induced electron oscillations which cannot radiate to the far-field because wavevector matching is not possible. We suggest that the energy from the fluorophores thought to be lost by lossy surface waves can be recovered as emission by adjustment of the sample to allow wavevector matching. The RP model provides a rational approach for designing fluorophore-metal configurations with the desired emissive properties and a basis for nanophotonic fluorophore technology.     

Review of Some Interesting Surface Plasmon Resonance-enhanced Properties of Noble Metal Nanoparticles and Their Applications to Biosystems

Noble metal, especially gold (Au) and silver (Ag) nanoparticles exhibit unique and tunable optical properties on account of their surface plasmon resonance (SPR). In this review, we discuss the SPR-enhanced optical properties of noble metal nanoparticles, with an emphasis on the recent advances in the utility of these plasmonic properties in molecular-specific imaging and sensing, photo-diagnostics, and selective photothermal therapy. The strongly enhanced SPR scattering from Au nanoparticles makes them useful as bright optical tags for molecular-specific biological imaging and detection using simple dark-field optical microscopy. On the other hand, the SPR absorption of the nanoparticles has allowed their use in the selective laser photothermal therapy of cancer. We also discuss the sensitivity of the nanoparticle SPR frequency to the local medium dielectric constant, which has been successfully exploited for the optical sensing of chemical and biological analytes. Plasmon coupling between metal nanoparticle pairs is also discussed, which forms the basis for nanoparticle assembly-based biodiagnostics and the plasmon ruler for dynamic measurement of nanoscale distances in biological systems.     

Role of Stopband and Localized Surface Plasmon Resonance in Raman Scattering from Metallo-Dielectric Photonic Crystals

Self-assembled photonic crystals grown from different colloidal sizes are coated with gold nanoparticles preferentially on their surface. The effect of localized surface plasmon resonance and the photonic stopband on the Raman scattering from these crystals is analyzed from the angle-dependent scattering measurements. The coupling of photonic and plasmonic modes at the surface of the photonic crystal is verified by measuring the increment in Raman scattering from the crystals containing the gold nanoparticles, and this increment is found to follow the spectral trend of localized surface plasmon resonance.