Peptide‐Targeted Gold Nanoparticles for Photodynamic Therapy of Brain Cancer

Targeted drug delivery using epidermal growth factor peptide‐targeted gold nanoparticles (EGF_pep‐Au NPs) is investigated as a novel approach for delivery of photodynamic therapy (PDT) agents, specifically Pc 4, to cancer. In vitro studies of PDT show that EGF_pep‐Au NP‐Pc 4 is twofold better at killing tumor cells than free Pc 4 after increasing localization in early endosomes. In vivo studies show that targeting with EGF_pep‐Au NP‐Pc 4 improves accumulation of fluorescence of Pc 4 in subcutaneous tumors by greater than threefold compared with untargeted Au NPs. Targeted drug delivery and treatment success can be imaged via the intrinsic fluorescence of the PDT drug Pc 4. Using Pc 4 fluorescence, it is demonstrated in vivo that EGF_pep‐Au NP‐Pc 4 impacts biodistribution of the NPs by decreasing the initial uptake by the reticuloendothelial system (RES) and by increasing the amount of Au NPs circulating in the blood 4 h after IV injection. Interestingly, in vivo PDT with EGF_pep‐Au NP‐Pc 4 results in interrupted tumor growth when compared with EGF_pep‐Au NP control mice when selectively activated with light. These data demonstrate that EGF_pep‐Au NP‐Pc 4 utilizes cancer‐specific biomarkers to improve drug delivery and therapeutic efficacy over untargeted drug delivery.     

金纳米粒子的放射增敏效应研究

系统阐述了与金纳米粒子(GNPs) 放射增敏效应相关实验的方法与结果、影响GNPs 放射增敏的因素、GNPs 放射增敏的细胞和动物实验表现及其相关机制。同时结合相关实验,分析和比较了15 nm 柠檬酸钠包被的GNPs 的放射增敏效应,发现GNPs 在高LET 的碳离子束和低LET 的X射线辐照下对Hela细胞的杀伤力随其浓度的增加而增大;在50% 的细胞存活率下,当GNPs 的质量浓度为7.5 g/mL时,其X射线的剂量减少率和碳离子的相对生物学效应值(RBE) 的增加率达到了最大,分别为65.3% 和43.6%,同时GNPs 共培养细胞24 和48 h 后,未出现细胞周期同步化的现象。This paper describes the methods and results of the previous experiments, the experimental phenomena of the cell and animal tests and the relative mechanisms on the radiosensitizing effect of GNPs. Together with our experiments, the radiosensitizing effects of 15 nm citrate-capped GNPs and related mechanisms are analyzed and compared, finding that Hela cell killing of GNPs increase along with their concentration after exposure to high- and low-LET radiation such as carbon ions and X-rays. In addition, the percentages of dose reduction of the X-rays and RBE increment of the carbon ions reached their maximums 65.3% and 43.6%, respectively,at 50% survival level when Hela cells were pre-treated with 7.5 g/mL GNPs. Moreover, Hela cells showed no cell-cycle synchronization after 24 and 48 h exposure to GNPs.     

金银核壳结构复合纳米颗粒的消光特性研究

利用离散偶极近似(Discrete Dipole Approximation-DDA)算法,从理论上模拟分析了金银核壳结构复合纳米颗粒的消光光谱以及不同核壳厚度、不同介质折射率情况下峰位的变化情况。研究结果表明,随着壳层厚度的增加,复合纳米颗粒的消光谱线先逐渐形成两个与单质金属纳米颗粒相似的消光峰,后又逐渐合为一个半峰宽度较宽的消光峰;在不同介质环境中复合纳米颗粒的消光峰都随着介电常数的增大出现红移;无论是作为核层还是壳层,银对总体消光谱线的作用都要比金强。     

Nucleation of Polypropylene Crystallization with Gold Nanoparticles. Part 2: Relation between Particle Morphology and Nucleation Activity

The influence of gold nanoparticle morphology on nucleation of isotactic polypropylene (PP) crystallization was investigated. Previous experiments indicated certain nucleation activity of gold nanoparticles, varying with their size. In this work, eight types of gold micro/nanoparticles were used: vacuum-sputtered nanostructures (nanoparticles, nanoislands, and nanolayers), chemically prepared isometric gold nanocrystals (5, 20, and 100 nm diameters), and two types of gold microcrystals with well-developed crystal facets [with (100) and (111) facets, respectively]. To minimize the effect of particle agglomeration, we used our recently introduced sandwich method, in which the nucleating agent was deposited between thin PP films and the nucleation was evaluated by polarized light microscopy (PLM), X-ray scattering (WAXS), and differential scanning calorimetry (DSC). The nucleation activity of Au particles in PP was lower than it might be expected from the previous studies and depended on their morphology. The nucleation activity of Au microcrystals with well-developed facets was higher than the activity of non-faceted Au nanocrystals.     

Surface Modification of Gold Nanoprisms and Their Self-Assembly with Nanospheres

Controlled surface modification of gold particles is of central importance for the preparation of functional nano-objects, which can be used both in fundamental research and in advanced photonic or nanomedicine applications. In this study, the surface modification of gold nanoprisms using different thiols, namely cysteamine, (16-mercaptohexadecyl)trimethylammonium bromide (MTAB), and α-methoxy-ω-mercapto polyethylene glycol (mPEG-SH (5000 Da)) is investigated. The aim is to prepare binary surface-modified thiol/PEG patchy gold nanoprisms, where the tips/edges and the face regions of the particles are covered by different thiol moieties. By investigating the time evolution of the prisms’ extinction spectra at different capping ligand concentration levels, the conditions to prepare such “patchy” particles are identified. While significantly faster adsorption kinetics are observed for MTAB compared to cysteamine, both molecule types can be used to prepare binary surface-modified thiol/PEG particles. Prisms modified with only MTAB or PEG and subsequently assembled with negatively charged spheres show that MTAB forms hetero-aggregates with the spheres, while PEG prevents particle attachment. For thiol (cysteamine or MTAB)/PEG binary surface-modified prisms, it is found that the efficiency of sphere attachment at the tip/side region during self-assembly is rather low, most likely due to the presence of PEG.     

Facile Functionalization of Gold Nanoparticles with PLGA Polymer Brushes and Efficient Encapsulation into PLGA Nanoparticles: Toward Spatially Precise Bioimaging of Polymeric Nanoparticles

Nanocarriers prepared from poly(lactide‐co‐glycolide) (PLGA) have broad biomedical applications. Understanding their cellular uptake and distribution requires appropriate visualization in complex biological compartments with high spatial resolution, which cannot be offered by traditional imaging techniques based on fluorescent or radioactive probes. Herein, the encapsulation of gold nanoparticles (GNPs) into PLGA nanoparticles is proposed, which should allow precise spatial visualization in cells using electron microscopy. Available protocols for encapsulating GNPs into polymeric matrices are limited and associated with colloidal instability and low encapsulation efficiency. In this report, the following are described: 1) a facile protocol to functionalize GNPs with PLGA polymer followed by 2) encapsulation of the prepared PLGA‐capped GNPs into PLGA nanocarriers with 100% encapsulation efficiency. The remarkable encapsulation of PLGA‐GNPs into PLGA matrix obeys the general rule in chemistry “like dissolves like” as evident from poor encapsulation of GNPs capped with other polymers. Moreover, it is shown that how the encapsulated gold nanoparticles serve as nanoprobes to visualize PLGA polymeric hosts inside cancer cells at the spatial resolution of the electron microscope. The described methods should be applicable to a wide range of inorganic nanoprobes and provide a new method of labeling pharmaceutical polymeric nanocarriers to understand their biological fate at high spatial resolution.     

Systematic Control of Size and Morphology in the Synthesis of Gold Nanoparticles

The synthesis of gold nanoparticles (Au NPs) capped by poly(1‐vinylpyrrolidin‐2‐one (PVP, average  = 10 000 kDa) yields moderately dispersed (6–8.5 nm) product with limited morphological control while larger NPs (15–20 nm) are reliably prepared using trisodium citrate (Na₃Cit) as a reductant/capping agent. Excellent size control in the intermediate 10 nm regime is achieved by hybridizing these methodologies, with highly monodisperse, polycrystalline Au NPs forming. For a Na₃Cit:PVP:Au ratio of 3.5:3.5:1, anisotropic NPs with an aspect ratio of 1.8:1 suggest the systematic agglomeration of NP pairs. Enhanced control of NP morphology is allowed by the 1,2‐tetradecanediol reduction of Au^III in the presence of straight chain, molecular anti‐agglomerants. Last, ligand substitution is used to controllably grow preformed Au seeds. In spite of the extended growth phase used, the replacement of phosphine by 1‐pentadecylamine affords highly monodisperse, cuboidal NPs containing a single clearly visible twinning plane. The allowance of particle growth parallel to this close‐packed plane explains the remarkable particle morphology.     

超薄金壳包覆NaYF4:Yb,Er@SiO2纳米结构的可控合成与表面增强上转换荧光

利用原位还原法成功制备了尺寸均一、超薄完整金壳包覆的NaYF₄:Yb,Er@SiO₂@Au（NSA）纳米结构,其XRD、TEM、EDX、HRTEM-HAADF、Mapping及吸收光谱表征结果表明,SiO₂壳及纳米金壳的平均厚度分别约为5 nm和2 nm。在980 nm连续激光激发下,系统研究了核壳结构的上转换荧光强度与氯金酸浓度的依赖关系。稳态光谱结果显示,NSA与仅SiO₂包覆样品（NS）相比Er³⁺的红绿荧光强度均增强了~2.8倍。通过分析上转换荧光动力学过程及利用FDTD方法模拟,讨论了表面等离激元增强上转换荧光的机制。     

Fluorescent properties and symmetry of the monodeprotonated form of 5,10,15,20-tetrakis-(4-N-methylpyridyl)-porphyrin

The spectral and kinetic properties of the monodeprotonated form of the cationic 5,10,15,20-tetrakis(4-Nmethylpyridyl) porphyrin (H₂TMPyP) in solution are studied. The experimental results obtained are interpreted based on the four-orbital Gouterman model. It is established that the monodeprotonated form HTMPyP⁻ can be assigned to the D4h symmetry point group, and has spectral and photophysical characteristics similar to the characteristics of the fluorescent metal complexes of H₂TMPyP with relatively low electronegativity of the chelated metal ion. It is hypothesized that formation of the monodeprotonated form HTMPyP⁻ is accompanied by a decrease in the oxidation potential of the porphyrin molecule. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 5, pp. 613–619, September–October, 2006.     

Comparing the Contribution of Visible‐Light Irradiation,Gold Nanoparticles,and Titania Supports in Photocatalytic Nitroaromatic Coupling and Aromatic Alcohol Oxidation

Under visible‐light irradiation, gold nanoparticles (Au NPs) supported by titania (TiO₂) nanofibers show excellent activity and high selectivity for both reductive coupling of nitroaromatics to corresponding azobenzene or azoxylbenzene and selective oxidation of aromatic alcohols to corresponding aldehydes. The Au NPs act as active centers mainly due to their localized surface plasmon resonance (LSPR) effect. They can effectively couple the photonic energy and thermal energy to enhance reaction efficiency. Visible‐light irradiation has more influence on the reduction than on the oxidation, lowering the activation energy by 24.7 kJ mol^?1 and increasing the conversion rate by 88% for the reductive coupling, compared to merely 8.7 kJ mol^?1 and 46% for the oxidation. Furthermore, it is found that the conversion of nitroaromatics significantly depends on the particle size and specific surface area of supported Au NPs; and the catalyst on TiO₂(B) support outperforms that on anatase phase with preferable ability to activate oxygen. In contrast, for the selective oxidation, the effect of surface area is less prominent and Au NPs on anatase exhibit higher photo‐catalytic activity than other TiO₂ phases. The catalysts can be recovered efficiently because the Au NPs stably attach to TiO₂ supports by forming a well‐matched coherent interface observed via high‐resolution TEM.     

Encapsulation of Co3O4 Nanoparticles Inside CeO2 Nanotubes: An Efficient Biocatalyst for the Ultrasensitive Detection of Ascorbic Acid

A quick and sensitive detection of ascorbic acid (AA) is essential in the fields of biosensing and disease diagnosis. In this work, an effective approach combined with electrospinning, chemical bath deposition, and calcination process is developed to encapsulate Co₃O₄ nanoparticle into CeO₂ nanotubes as efficient peroxidase mimics for the detection of AA. The peroxidase‐like catalytic activity of the as‐prepared Co₃O₄@CeO₂ nanotubes is much higher than that of individual Co₃O₄ nanofibers and CeO₂ nanotubes alone due to the synergistic effect between the two components. Owing to the superior catalytic efficiency of the prepared Co₃O₄@CeO₂ nanotubes, a colorimetric route for the rapid and accurate detection of AA with a detection limit of 0.73 × 10⁻⁹m with a wide linear range from 0 to 0.8 × 10⁻⁶m is demonstrated. This detection limit is much better than the previous reports based on the enzyme‐like catalytic systems. In addition, a good selectivity toward the detection of AA over amino acids, common ions, dopamine, and uric acid is achieved. This study offers a new approach for the fabrication of Co₃O₄@CeO₂ nanotubes as sensing platform toward the detection of AA, which presents promising potential applications in biosensing, environmental monitoring, and medical diagnostics.     

High–Yield Production of Uniform Gold Nanoparticles with Sizes from 31 to 577 nm via One‐Pot Seeded Growth and Size‐Dependent SERS Property

In this work, uniform, quasi‐spherical gold nanoparticles (Au NPs) with sizes of 31–577 nm are prepared via one‐pot seeded growth with the aid of tris‐base (TB). Distinct from the seeded growth methods available in literature, the present method can be simply implemented by subsequently adding the aqueous dispersion of the 17 nm Au‐NP seeds and the aqueous solution of HAuCl₄ into the boiling aqueous TB solution. It is found that at the optimal pH range, the sizes of the final Au NPs and their concentrations are simply controlled by either the particle number of the Au seed dispersion or the concentration of the HAuCl₄ solution, while the latter enables us to produce large Au NPs at very high concentration. Moreover, as‐prepared Au NPs of various sizes are coated on glass substrates to test their surface‐enhanced Raman scattering (SERS) activities by using 4‐aminothiophenol (4‐ATP) molecules as probes, which exhibit “volcano type” dependence on the Au NP sizes at fixed excitation wavelength. Furthermore, the Au NPs with sizes of ≈97 and 408 nm exhibit the largest SERS enhancement at the excitation wavelength of 633 and 785 nm, respectively.     

Analysis of the Effects of Protic,Aprotic, and Multi-Component Solvents on the Fluorescence Emission of Naphthalene and its Exciplex with Triethylamine

The emission spectra of naphthalene (NP)–triethylamine (TEA) systems were measured under steady-state illumination conditions in some protic and aprotic solvent-tetrahydrofuran (THF) mixtures. The fluorescence spectrum of the NP–TEA system in THF could be separated into two component bands (band A at 329 nm (fluorescence of NP) and band B at 468 nm (emission from an intermolecular exciplex)). The intensities of bands A and B decreased with increasing solvent polarity. The intensity of band B also decreased owing to the hydrogen-bonding interaction between TEA and protic solvents, but in this case the intensity of band A increased. The decrease in the intensity of band A with increasing solvent polarity is considered to be caused by the enhanced formation of an ion-pair parallel to the formation of an exciplex with increasing solvent polarity. The decrease in the intensity of band B is considered to be caused by the enhanced formation of ion-pair both parallel to and through the formation of the exciplex. The increase in the intensity of band A and the decrease in that of band B upon the addition of protic solvents is caused by the decrease in the concentration of free TEA. Acetonitrile only has a polar effect and trichloroacetic acid only has a hydrogen-bonding (protonation) effect, while alcohols have both the effects.     

Synergistic Action of Alginate Chemical Reduction and Laser Irradiation for the Formation of Au Nanoparticles with Controlled Dimensions

Freestanding natural polymeric films with homogeneous dispersion of gold nanoparticles (Au NPs) are obtained via in situ reduction of gold(III) chloride trihydrate by sodium alginate (SA) biopolymer matrix, during water evaporation without the use of additional reducing agents. The size and size distribution of the prepared Au NPs can be tuned by changing the concentration of the precursor and/or the procedure of the films’ preparation. The nanocomposite films after preparation are stable in ambient conditions and can be used without the need of further processing, or can be redissolved in water. In the case of water dissolution, the aqueous solutions are irradiated with UV laser pulses turning the previously formed Au NPs into smaller ones with narrow size distributions through photofragmentation. This technique is proposed as a green way of synthesizing Au NPs of tunable size in aqueous solution of alginate, or incorporated in alginate freestanding polymeric films, that due to their biocompatibility can be used as passive labels or active sensors in biomedical applications.     

An Improved Method for Site‐Specific End Modification of Zeolite L for the Formation of Zeolite L and Gold Nanoparticle Self‐Assembled Structures

The ability to site‐selectively modify micro‐ and nanosized particles has allowed for directed self‐assembly in two and three dimensions. Site‐selective modification of particles can be a complicated task requiring the pre‐organization of particles or enhanced particle fabrication methods. The aluminum silicate, zeolite L has been reported to undergo site‐specific modification at the zeolite channel entrances, post‐fabrication in a solution‐based method. The process by which the channel entrances are site selectively modified is explored here. The preliminary step of charging the zeolite channels with aqueous acid allows for catalysis of covalent bond formation at the channel entrances. Three new end‐specific modification reagents are described based on silanol and silyl ether functional groups. These reagents are purified by column chromatography and characterized by¹H NMR spectroscopy and high resolution mass spectrometry (HRMS); they provide for reliable end modification of zeolites L. Preferential reactivity at the channel entrances is also observed. The utility of the approach is demonstrated by modifying zeolite L with adamantane at the channel entrances. Site‐specific self‐assembly with β‐cyclodextrin coated gold nanoparticles can be triggered with a chemical stimulus. The resulting multivalent host‐guest interactions give gold clustered nanoparticles at the ends of the micrometer‐sized zeolites.     

Determination of Conjugation Efficiency of Antibodies and Proteins to the Superparamagnetic Iron Oxide Nanoparticles by Capillary Electrophoresis with Laser-Induced Fluorescence Detection

The method based on capillary electrophoresis with laser-induced fluorescence detection (CE/LIF) was developed for determination of magnetic iron oxide nanoparticles (hydrodynamic diameters of 100 nm) functionalized with molecules containing primary amino groups. The magnetic nanoparticles with carboxylic or aminopropyl-trimethoxysilane groups at their surface were conjugated to the model proteins (bovine serum albumin, BSA; streptavidin or goat anti-rabbit immunoglobulin G, IgG) using carbodiimide as a zero-length cross-linker.The nanoparticle–protein conjugates (hydrodynamic diameter 163–194 nm) were derivatized with naphthalene-2,3-dicarboxaldehyde reagent and separated by CE/LIF with a helium–cadmium laser (excitation at 442 nm, emission at 488 nm). The separations were carried out by using a fused-silica capillary (effective length 48 cm, inner diameter 75 um) and 100 mM sodium borate buffer (pH 9.2), the potential was 30 kV. The detection limit for BSA-conjugate was 1.3 pg/10 nl, i.e. about 20 amol. The present method provides an efficient and fast tool for sensitive determination of the efficacy of biomolecular functionalization of magnetic nanoparticles. The CE/LIF technique requires only negligible sample volumes for analysis, which is especially suitable for controlling the process of preparation of functionalized nanoparticles with unique properties aimed to be used for diagnostic or therapeutic purposes.     

Effect of K4FE(CN)6 and K3FE(CN)6 on TICT Dual Fluorescence of Sodium p-Dimethylaminobenzoate in Cetyltrimethylammonium Chloride Micelle. Identification of the Magenetic Effect in TICT Process

Comparison of the effects of K₄Fe(CN)₆ and K₃Fe(CN)₆ on TICT dual fluorescence of sodium p-dimethylaminobenzoate (SDMAB) in cetyltrimethyl ammonium chloride (CTAC) micelle yields a conclusion that the presence of a magnetic effect un favors the TICT process, which is verified by inserting the sample in a stationary magnetic field of 100G in which a decrease in the relative quantum yield of TICT state is observed.     

惰性稀土离子和抗衡离子对2-噻吩乙醛酸-铕配合物荧光性能的影响

研究了惰性稀土离子和抗衡离子对一系列2-噻吩乙醛酸-铕配合物荧光性能的影响。分别在2-噻吩乙醛酸-邻菲罗啉-铕和2-噻吩乙醛酸-三苯基氧化膦-铕两个体系中按不同比例掺入钇和钆,研究了它们的荧光光谱。结果表明,钇的加入对2-噻吩乙醛酸-邻菲罗啉-铕体系的荧光强度有很强的敏化作用,并且随加入量的增加,这种敏化作用逐渐增强。钇的加入对2-噻吩乙醛酸-三苯基氧化膦-铕体系则呈现出弱的敏化作用,且在一定程度上具有猝灭作用,但这两种作用都是很微小的。钆在少量加入时对2-噻吩乙醛酸-三苯基氧化膦-铕体系具有猝灭作用,当大量加入时则呈现出很强的敏化作用。不同的抗衡离子对配合物的影响是明显的。在二元配合物中,氯化物体系的固体荧光强度最大;在三元配合物中,硝酸盐体系的固体荧光强度最大。     

改进型M-P神经网络在能量色散X荧光分析测定铅锌矿元素含量的应用研究

以新疆西天山铅锌矿样品的Cu,Fe,Pb等元素X荧光测量数据做训练样本,McCulloch-Pitts神经网络(M-P神经网络)为基础,基体效应为依据,建立新的神经网络模型对Zn进行定量预测。结果预测值与测量值的相对误差在<5%。此方法可较准确,快速的应用于现场X荧光测定,为X荧光光谱信息修正提供一种新方法。