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1.  Nanoscaled alloy formation from self-assembled elemental Co nanoparticles on top of Pt films 
The thermally activated formation of nanoscale CoPt alloys was investigated, after deposition of self-assembled Co nanoparticles on textured Pt(111) and epitaxial Pt(100) films on MgO(100) and SrTiO3(100) substrates, respectively. For this purpose, metallic Co nanoparticles (diameter 7 nm) were prepared with a spacing of 100 nm by deposition of precursor-loaded reverse micelles, subsequent plasma etching and reduction on flat Pt surfaces. The samples were then annealed at successively higher temperatures under a H2 atmosphere, and the resulting variations of their structure, morphology and magnetic properties were characterized. We observed pronounced differences in the diffusion and alloying of Co nanoparticles on Pt films with different orientations and microstructures. On textured Pt(111) films exhibiting grain sizes (20–30 nm) smaller than the particle spacing (100 nm), the formation of local nanoalloys at the surface is strongly suppressed and Co incorporation into the film via grain boundaries is favoured. In contrast, due to the absence of grain boundaries on high quality epitaxial Pt(100) films with micron-sized grains, local alloying at the film surface was established. Signatures of alloy formation were evident from magnetic investigations. Upon annealing to temperatures up to 380 °C, we found an increase both of the coercive field and of the Co orbital magnetic moment, indicating the formation of a CoPt phase with strongly increased magnetic anisotropy compared to pure Co. At higher temperatures, however, the Co atoms diffuse into a nearby surface region where Pt-rich compounds are formed, as shown by element-specific microscopy.
PMCID: PMC3190617  PMID: 22003453
alloy; Co; CoPt; epitaxy; HRTEM; magnetometry; nanoparticles; Pt; XMCD
2.  Current state of laser synthesis of metal and alloy nanoparticles as ligand-free reference materials for nano-toxicological assays 
Due to the abundance of nanomaterials in medical devices and everyday products, toxicological effects related to nanoparticles released from these materials, e.g., by mechanical wear, are a growing matter of concern. Unfortunately, appropriate nanoparticles required for systematic toxicological evaluation of these materials are still lacking. Here, the ubiquitous presence of surface ligands, remaining from chemical synthesis are a major drawback as these organic residues may cause cross-contaminations in toxicological studies. Nanoparticles synthesized by pulsed laser ablation in liquid are a promising alternative as this synthesis route provides totally ligand-free nanoparticles. The first part of this article reviews recent methods that allow the size control of laser-fabricated nanoparticles, focusing on laser post irradiation, delayed bioconjugation and in situ size quenching by low salinity electrolytes. Subsequent or parallel applications of these methods enable precise tuning of the particle diameters in a regime from 4–400 nm without utilization of any artificial surface ligands. The second paragraph of this article highlights the recent progress concerning the synthesis of composition controlled alloy nanoparticles by laser ablation in liquids. Here, binary and ternary alloy nanoparticles with totally homogeneous elemental distribution could be fabricated and the composition of these particles closely resembled bulk implant material. Finally, the model AuAg was used to systematically evaluate composition related toxicological effects of alloy nanoparticles. Here Ag+ ion release is identified as the most probable mechanism of toxicity when recent toxicological studies with gametes, mammalian cells and bacteria are considered.
PMCID: PMC4168911  PMID: 25247135
albumin; gold-silver; implant alloy; laser ablation; nickel-titanium; size control; wear debris
3.  Rapid Synthesis of Monodisperse Au Nanospheres through a Laser Irradiation -Induced Shape Conversion, Self-Assembly and Their Electromagnetic Coupling SERS Enhancement 
Scientific Reports  2015;5:7686.
We develop a facile and effective strategy to prepare monodispersed Au spherical nanoparticles by two steps. Large-scale monocrystalline Au nanooctahedra with uniform size were synthesized by a polyol-route and subsequently Au nanoparticles were transformed from octahedron to spherical shape in a liquid under ambient atmosphere by non-focused laser irradiation in very short time. High monodipersed, ultra-smooth gold nanospheres can be obtained by simply optimizing the laser fluence and irradiation time. Photothermal melting-evaporation model was employed to get a better understanding of the morphology transformation for the system of nanosecond pulsed-laser excitation. These Au nanoparticles were fabricated into periodic monolayer arrays by self-assembly utilizing their high monodispersity and perfect spherical shape. Importantly, such Au nanospheres arrays demonstrated very good SERS enhancement related to their periodic structure due to existence of many SERS hot spots between neighboring Au nanospheres caused by the electromagnetic coupling in an array. These gold nanospheres and their self-assembled arrays possess distinct physical and chemical properties. It will make them as an excellent and promising candidate for applying in sensing and spectroscopic enhancement, catalysis, energy, and biology.
PMCID: PMC4286736  PMID: 25566872
4.  Engineering Au Nanoparticle Arrays on SiO2 Glass by Pulsed UV Laser Irradiation 
Plasmonics (Norwell, Mass.)  2012;8(1):105-113.
We study semi-regular arrays of Au nanoparticles (NP) obtained via UV laser irradiation of thin Au films on glass substrate. The NP structures are prepared from films of a thickness up to 60 nm produced by discharge sputtering or pulsed laser deposition, and annealed by nanosecond laser pulses at 266 or 308 nm, respectively, at fluencies in the range of 60–410 mJ/cm2. For the rare- and close-packed NP structures, consistent description of optical properties is derived from microscopic observation, measurements of the absorption, and Raman spectra, and modeling of the near-field intensity distributions. The absorption bands centered at 540–570 nm are ascribed to resonant absorption of the surface plasmons. For the band positions, half widths, and intensities, the dependence on the NP shape (partial spheres), size, size distribution, and also excitation energy is observed. The structures are characterized by markedly reduced dephasing times of ∼3 fs. It is shown, that laser annealing of thin Au films provides reliable and cost effective method for controlled preparation of semi-regular NP arrays favorable for photonic applications.
PMCID: PMC3597268  PMID: 23503766
Au nanoparticles; Laser annealing; Semi-regular nanostructures; Surface plasmon resonance
5.  Bimetallic non-alloyed NPs for improving the broadband optical absorption of thin amorphous silicon substrates 
Nanoscale Research Letters  2014;9(1):181.
We propose the use of bimetallic non-alloyed nanoparticles (BNNPs) to improve the broadband optical absorption of thin amorphous silicon substrates. Isolated bimetallic NPs with uniform size distribution on glass and silicon are obtained by depositing a 10-nm Au film and annealing it at 600°C; this is followed by an 8-nm Ag film annealed at 400°C. We experimentally demonstrate that the deposition of gold (Au)-silver (Ag) bimetallic non-alloyed NPs (BNNPs) on a thin amorphous silicon (a-Si) film increases the film's average absorption and forward scattering over a broad spectrum, thus significantly reducing its total reflection performance. Experimental results show that Au-Ag BNNPs fabricated on a glass substrate exhibit resonant peaks at 437 and 540 nm and a 14-fold increase in average forward scattering over the wavelength range of 300 to 1,100 nm in comparison with bare glass. When deposited on a 100-nm-thin a-Si film, Au-Ag BNNPs increase the average absorption and forward scattering by 19.6% and 95.9% compared to those values for Au NPs on thin a-Si and plain a-Si without MNPs, respectively, over the 300- to 1,100-nm range.
PMCID: PMC3990030  PMID: 24725390
Optics at surface; Surface plasmon resonance; Antireflection; Scattering light
6.  Nanoparticle Thin Films for Gas Sensors Prepared by Matrix Assisted Pulsed Laser Evaporation 
Sensors (Basel, Switzerland)  2009;9(4):2682-2696.
The matrix assisted pulsed laser evaporation (MAPLE) technique has been used for the deposition of metal dioxide (TiO2, SnO2) nanoparticle thin films for gas sensor applications. For this purpose, colloidal metal dioxide nanoparticles were diluted in volatile solvents, the solution was frozen at the liquid nitrogen temperature and irradiated with a pulsed excimer laser. The dioxide nanoparticles were deposited on Si and Al2O3 substrates. A rather uniform distribution of TiO2 nanoparticles with an average size of about 10 nm and of SnO2 nanoparticles with an average size of about 3 nm was obtained, as demonstrated by high resolution scanning electron microscopy (SEM-FEG) inspections. Gas-sensing devices based on the resistive transduction mechanism were fabricated by depositing the nanoparticle thin films onto suitable rough alumina substrates equipped with interdigitated electrical contacts and heating elements. Electrical characterization measurements were carried out in controlled environment. The results of the gas-sensing tests towards low concentrations of ethanol and acetone vapors are reported. Typical gas sensor parameters (gas responses, response/recovery time, sensitivity, and low detection limit) towards ethanol and acetone are presented.
PMCID: PMC3348821  PMID: 22574039
Nanoparticles; thin films; MAPLE; gas sensors
7.  Facile synthesis of pentacle gold–copper alloy nanocrystals and their plasmonic and catalytic properties 
Nature Communications  2014;5:4327.
The combination of gold and copper is a good way to pull down the cost of gold and ameliorate the instability of copper. Through shape control, the synergy of these two metals can be better exploited. Here, we report an aqueous phase route to the synthesis of pentacle gold–copper alloy nanocrystals with fivefold twinning, the size of which can be tuned in the range from 45 to 200 nm. The growth is found to start from a decahedral core, followed by protrusion of branches along twinning planes. Pentacle products display strong localized surface plasmon resonance peaks in the near-infrared region. Under irradiation by an 808-nm laser, 70-nm pentacle nanocrystals exhibit a notable photothermal effect to kill 4T1 murine breast tumours established on BALB/c mice. In addition, 70-nm pentacle nanocrystals show better catalytic activity than conventional citrate-coated 5-nm Au nanoparticles towards the reduction of p-nitrophenol to p-aminophenol by sodium borohydride.
Control over the size and shape of nanostructures is important for many applications but challenging, especially for bimetallic systems. Here, the authors report the size-controlled synthesis of star-shaped gold–copper nanocrystals and show their applications in catalysis and photothermal therapy.
PMCID: PMC4102124  PMID: 24999674
8.  Preparation and characterization of supported magnetic nanoparticles prepared by reverse micelles 
Monatomic (Fe, Co) and bimetallic (FePt and CoPt) nanoparticles were prepared by exploiting the self-organization of precursor loaded reverse micelles. Achievements and limitations of the preparation approach are critically discussed. We show that self-assembled metallic nanoparticles can be prepared with diameters d = 2–12 nm and interparticle distances D = 20–140 nm on various substrates. Structural, electronic and magnetic properties of the particle arrays were characterized by several techniques to give a comprehensive view of the high quality of the method. For Co nanoparticles, it is demonstrated that magnetostatic interactions can be neglected for distances which are at least 6 times larger than the particle diameter. Focus is placed on FePt alloy nanoparticles which show a huge magnetic anisotropy in the L10 phase, however, this is still less by a factor of 3–4 when compared to the anisotropy of the bulk counterpart. A similar observation was also found for CoPt nanoparticles (NPs). These results are related to imperfect crystal structures as revealed by HRTEM as well as to compositional distributions of the prepared particles. Interestingly, the results demonstrate that the averaged effective magnetic anisotropy of FePt nanoparticles does not strongly depend on size. Consequently, magnetization stability should scale linearly with the volume of the NPs and give rise to a critical value for stability at ambient temperature. Indeed, for diameters above 6 nm such stability is observed for the current FePt and CoPt NPs. Finally, the long-term conservation of nanoparticles by Au photoseeding is presented.
PMCID: PMC3045932  PMID: 21977392
Co; CoPt; core–shell particles; FePt; magnetic anisotropy; magnetic particles; plasma etching; reverse micelles; self-assembly
9.  Synthesis and characterization of potential iron–platinum drugs and supplements by laser liquid photolysis 
Highly crystalline nanospherical iron–platinum systems were produced by 248 nm laser irradiation of a liquid precursor at different laser fluences, ranging from 100–375 mJ/cm2. The influence of laser intensity on particle size, iron composition, and structure was systematically investigated. Different nanostructures of iron–platinum alloy and chemically disordered iron–platinum L10 phase were obtained without annealing. The prepared precursor solution underwent deep photolysis to polycrystalline iron–platinum nanoalloys through Fe(III) acetylacetonate and Pt(II) acetylacetonate. Fe(II) and Pt(I) acetylacetone decomposed into Fe0 and Pt0 nanoparticles. We found that the (001) diffraction peak shifted linearly to a lower angle, with the last peak shifting in opposition to the others. This caused the face-centered cubic L10 structure to change its composition according to laser fluence. The nanostructures were shown to contain iron and platinum only by energy-dispersive spectroscopy at several spots. The response of these iron–platinum nanoparticles to infrared depends on their stoichiometric composition, which is controlled by laser fluence.
PMCID: PMC3781719  PMID: 24198494
nanostructures; iron; platinum; nanoparticles; laser liquid photolysis; composition
10.  Laser Hybrid Micro/nano-structuring of Si Surfaces in Air and its Applications for SERS Detection 
Scientific Reports  2014;4:6657.
Surface enhanced Raman spectroscopy (SERS) has been widely investigated as an effective technique for low-concentration bio-chemical molecules detection. A rapid two-step approach to fabricate SERS substrates with high controllability in ambient air is developed. Dynamic laser ablation directly creates microgroove on the Si substrate. Meanwhile, nanoparticles are synthesized via the nucleation of laser induced plasma species and the air molecules. It configures the Si surface into four different regions decorated with nanoparticles at different sizes. With Ag film coating, these nanoparticles function as hotspots for SERS. Microsquare arrays are fabricated on the Si surface as large-area SERS substrates by the laser ablation in horizontal and vertical directions. In each microsquare, it exhibits quasi-3D structures with randomly arranged and different shaped nanoparticles aggregated in more than one layer. With Ag film deposition, uniform SERS signals are obtained by detecting the 4-methylbenzenethiol molecules. The SERS signal intensity is determined by the size and shape distributions of the nanoparticles, which depend on the laser processing parameters. With the optimal laser fluence, the SERS signals show a uniform enhancement factor up to 5.5 × 106. This provides a high-speed and low-cost method to produce SERS substrates over a large area.
PMCID: PMC4200404  PMID: 25324167
11.  Structure, morphology, and magnetic properties of Fe nanoparticles deposited onto single-crystalline surfaces 
Background: Magnetic nanostructures and nanoparticles often show novel magnetic phenomena not known from the respective bulk materials. In the past, several methods to prepare such structures have been developed – ranging from wet chemistry-based to physical-based methods such as self-organization or cluster growth. The preparation method has a significant influence on the resulting properties of the generated nanostructures. Taking chemical approaches, this influence may arise from the chemical environment, reaction kinetics and the preparation route. Taking physical approaches, the thermodynamics and the kinetics of the growth mode or – when depositing preformed clusters/nanoparticles on a surface – the landing kinetics and subsequent relaxation processes have a strong impact and thus need to be considered when attempting to control magnetic and structural properties of supported clusters or nanoparticles.
Results: In this contribution we focus on mass-filtered Fe nanoparticles in a size range from 4 nm to 10 nm that are generated in a cluster source and subsequently deposited onto two single crystalline substrates: fcc Ni(111)/W(110) and bcc W(110). We use a combined approach of X-ray magnetic circular dichroism (XMCD), reflection high energy electron diffraction (RHEED) and scanning tunneling microscopy (STM) to shed light on the complex and size-dependent relation between magnetic properties, crystallographic structure, orientation and morphology. In particular XMCD reveals that Fe particles on Ni(111)/W(110) have a significantly lower (higher) magnetic spin (orbital) moment compared to bulk iron. The reduced spin moments are attributed to the random particle orientation being confirmed by RHEED together with a competition of magnetic exchange energy at the interface and magnetic anisotropy energy in the particles. The RHEED data also show that the Fe particles on W(110) – despite of the large lattice mismatch between iron and tungsten – are not strained. Thus, strain is most likely not the origin of the enhanced orbital moments as supposed before. Moreover, RHEED uncovers the existence of a spontaneous process for epitaxial alignment of particles below a critical size of about 4 nm. STM basically confirms the shape conservation of the larger particles but shows first indications for an unexpected reshaping occurring at the onset of self-alignment.
Conclusion: The magnetic and structural properties of nanoparticles are strongly affected by the deposition kinetics even when soft landing conditions are provided. The orientation of the deposited particles and thus their interface with the substrate strongly depend on the particle size with consequences regarding particularly the magnetic behavior. Spontaneous and epitaxial self-alignment can occur below a certain critical size. This may enable the obtainment of samples with controlled, uniform interfaces and crystallographic orientations even in a random deposition process. However, such a reorientation process might be accompanied by a complex reshaping of the particles.
PMCID: PMC3045938  PMID: 21977415
epitaxy; iron; magnetic nanoparticles; Ni(111); RHEED; spontaneous self-alignment; STM; W(110); XMCD
12.  HREM Analysis of Graphite-Encapsulated Metallic Nanoparticles for Possible Medical Applications 
Ultramicroscopy  2013;134:167-174.
High resolution electron microscopy has been applied to study the structure of metallic nanoparticles. These have sparked considerable interest as contrast agents in the field of biological imaging, including in magnetic resonance imaging (MRI) and computed tomography (CT). Here, we describe a method of synthesizing sub-10nm superparamagnetic metal and alloy nanoparticles by reduction of metallic salts. Annealing at 900°C in a methane/hydrogen environment forms a thin graphitic-carbon shell which is expected to improve stability, biocompatibility, and functionalization. Subsequent high resolution electron microscopy verifies graphitization and allows for crystallographic analysis. Most particles consist of single crystals in the phase predicted for the bulk material at the annealing temperature. Electron energy loss spectroscopy, energy dispersive X-ray spectroscopy and lattice constant measurements show large variation in composition for alloy nanoparticles from a single synthesis. The magnetization relaxation time (T2) measurements demonstrate that Fe and AuFe nanoparticles compete with commercially available iron oxide MRI contrast agents. X-ray attenuation measurements of an AuFe alloy nanoparticle solution gave a relative radiodensity of 280 Hounsfield Units, demonstrating promise as a dual-purpose contrast agent in CT and MRI. Long term stability in an atmospheric environment was also tested, with no signs of corrosion or oxidation after several years of storage.
PMCID: PMC3769614  PMID: 23809196
Metallic nanoparticles; HREM; Computed tomography; Magnetic resonance imaging
13.  Synthesis of 3D nanostructured metal alloy of immiscible materials induced by megahertz-repetition femtosecond laser pulses 
Nanoscale Research Letters  2012;7(1):518.
In this work, we have proposed a concept for the generation of three-dimensional (3D) nanostructured metal alloys of immiscible materials induced by megahertz-frequency ultrafast laser pulses. A mixture of two microparticle materials (aluminum and nickel oxide) and nickel oxide microparticles coated onto an aluminum foil have been used in this study. After laser irradiation, three different types of nanostructure composites have been observed: aluminum embedded in nickel nuclei, agglomerated chain of aluminum and nickel nanoparticles, and finally, aluminum nanoparticles grown on nickel microparticles. In comparison with current nanofabrication methods which are used only for one-dimensional nanofabrication, this technique enables us to fabricate 3D nanostructured metal alloys of two or more nanoparticle materials with varied composite concentrations under various predetermined conditions. This technique can lead to promising solutions for the fabrication of 3D nanostructured metal alloys in applications such as fuel-cell energy generation and development of custom-designed, functionally graded biomaterials and biocomposites.
PMCID: PMC3599459  PMID: 22999219
3D nanostructured metal alloy; Femtosecond laser pulses; Aluminum and nickel oxide; Ultrafast laser thermal effects
14.  Effects of crystallization and dopant concentration on the emission behavior of TiO2:Eu nanophosphors 
Uniform, spherical-shaped TiO2:Eu nanoparticles with different doping concentrations have been synthesized through controlled hydrolysis of titanium tetrabutoxide under appropriate pH and temperature in the presence of EuCl3·6H2O. Through air annealing at 500°C for 2 h, the amorphous, as-grown nanoparticles could be converted to a pure anatase phase. The morphology, structural, and optical properties of the annealed nanostructures were studied using X-ray diffraction, scanning electron microscopy, energy-dispersive X-ray spectroscopy [EDS], and UV-Visible diffuse reflectance spectroscopy techniques. Optoelectronic behaviors of the nanostructures were studied using micro-Raman and photoluminescence [PL] spectroscopies at room temperature. EDS results confirmed a systematic increase of Eu content in the as-prepared samples with the increase of nominal europium content in the reaction solution. With the increasing dopant concentration, crystallinity and crystallite size of the titania particles decreased gradually. Incorporation of europium in the titania particles induced a structural deformation and a blueshift of their absorption edge. While the room-temperature PL emission of the as-grown samples is dominated by the 5D0 - 7Fj transition of Eu+3 ions, the emission intensity reduced drastically after thermal annealing due to outwards segregation of dopant ions.
PMCID: PMC3260088  PMID: 22214494
titania nanoparticles; europium doping; optical properties; photoluminescence
15.  Three strategies to stabilise nearly monodispersed silver nanoparticles in aqueous solution 
Nanoscale Research Letters  2012;7(1):151.
Silver nanoparticles are extensively used due to their chemical and physical properties and promising applications in areas such as medicine and electronics. Controlled synthesis of silver nanoparticles remains a major challenge due to the difficulty in producing long-term stable particles of the same size and shape in aqueous solution. To address this problem, we examine three strategies to stabilise aqueous solutions of 15 nm citrate-reduced silver nanoparticles using organic polymeric capping, bimetallic core-shell and bimetallic alloying. Our results show that these strategies drastically improve nanoparticle stability by distinct mechanisms. Additionally, we report a new role of polymer functionalisation in preventing further uncontrolled nanoparticle growth. For bimetallic nanoparticles, we attribute the presence of a higher valence metal on the surface of the nanoparticle as one of the key factors for improving their long-term stability. Stable silver-based nanoparticles, free of organic solvents, will have great potential for accelerating further environmental and nanotoxicity studies.
PACS: 81.07.-b; 81.16.Be; 82.70.Dd.
PMCID: PMC3351018  PMID: 22356679
silver nanoparticles; stability; functionalisation; monodispersed; aging; toxicity.
16.  The preparation and characterization of folate-conjugated human serum albumin magnetic cisplatin nanoparticles☆ 
Journal of Biomedical Research  2010;24(1):26-32.
Nanoparticles are becoming an important method of targeted drug delivery. To evaluate the importance of folate-conjugated human serum albumin (HSA) magnetic nanoparticles (Folate-CDDP/HSA MNP), we prepared drug-loaded Folate-CDDP/HSA MNPs and characterized their features.
First, folate was conjugated with HSA under the effect of a condensing agent, and the conjugating rate was evaluated by a colorimetric method using 2, 4, 6 - trinitrobenzene sulfonic acid. Second, under N2 gas, Fe3O4 magnetic nanomaterials were prepared and characterized by using transmission electron microscopy (TEM), SEM-EDS and X-ray diffraction (XRD). Finally, Folate-CDDP/HSA MNP was prepared by using a solvent evaporation technique. TEM was used to observe particle morphology. The particle size and distribution of the prepared complexes were determined by a Laser particle size analyzer. Drug loading volume and drug release were investigated by a high performance liquid chromatography method (HPLC) in vitro.
We successfully prepared folate-conjugated HSA and its conjugating rate was 27.26 µg/mg. Under TEM, Fe3O4 magnetic nanoparticles were highly electron density and had an even size distribution in the range of 10-20 nm. It was confirmed by SEM-EDS and XRD that Fe3O4 magnetic nanoparticles had been successfully prepared. Under TEM, drug-loaded magnetic nanoparticles were observed, which had a round shape, similar uniform size and smooth surface. Their average size was 79 nm which was determined by laser scattering, and they exhibited magnetic responsiveness. Encapsulation efficiency was 89.75% and effective drug loading was calculated to be 15.25%. The release results in vitro showed that the half release time (t½) of cisplatin in cisplatin Solution and Folate-CDDP/HSA MNP was 65 min and 24 h respectively, which indicated that microspheres had an obvious effect of sustained-release.
Folate-CDDP/HSA MNPs were prepared successfully. The preparation process and related characteristics data provided a foundation for further study, including the mechanism of the nanoparticles distribution in vivo and their intake by tumor cells.
PMCID: PMC3596532  PMID: 23554608
cisplatin; folate; albumin magnetic nanoparticles; conjugate
17.  Chloroplasts-mediated biosynthesis of nanoscale Au-Ag alloy for 2-butanone assay based on electrochemical sensor 
Nanoscale Research Letters  2012;7(1):475.
We reported a one-pot, environmentally friendly method for biosynthesizing nanoscale Au-Ag alloy using chloroplasts as reducers and stabilizers. The prepared nanoscale Au-Ag alloy was characterized by UV–visible spectroscopy, X-ray diffraction (XRD) and high resolution transmission electron microscopy (HR-TEM). Fourier transform infrared spectroscopy (FTIR) analysis was further used to identify the possible biomolecules from chloroplasts that are responsible for the formation and stabilization of Au-Ag alloy. The FTIR results showed that chloroplast proteins bound to the nanoscale Au-Ag alloy through free amino groups. The bimetallic Au-Ag nanoparticles have only one plasmon band, indicating the formation of an alloy structure. HR-TEM images showed that the prepared Au-Ag alloy was spherical and 15 to 20 nm in diameter. The high crystallinity of the Au-Ag alloy was confirmed by SAED and XRD patterns. The prepared Au-Ag alloy was dispersed into multiwalled carbon nanotubes (MWNTs) to form a nanosensing film. The nanosensing film exhibited high electrocatalytic activity for 2-butanone oxidation at room temperature. The anodic peak current (Ip) has a linear relationship with the concentrations of 2-butanone over the range of 0.01% to 0.075% (v/v), when analyzed by cyclic voltammetry. The excellent electronic catalytic characteristics might be attributed to the synergistic electron transfer effects of Au-Ag alloy and MWNTs. It can reasonably be expected that this electrochemical biosensor provided a promising platform for developing a breath sensor to screen and pre-warn of early cancer, especially gastric cancer.
PMCID: PMC3506472  PMID: 22916797
Chloroplasts; Au-Ag alloy; Nanosensing film
18.  The Surprising in Vivo Instability of Near-IR-Absorbing Hollow Au–Ag Nanoshells 
ACS Nano  2014;8(4):3222-3231.
Photothermal ablation based on resonant illumination of near-infrared-absorbing noble metal nanoparticles that have accumulated in tumors is a highly promising cancer therapy, currently in multiple clinical trials. A crucial aspect of this therapy is the nanoparticle size for optimal tumor uptake. A class of nanoparticles known as hollow Au (or Au–Ag) nanoshells (HGNS) is appealing because near-IR resonances are achievable in this system with diameters less than 100 nm. However, in this study, we report a surprising finding that in vivo HGNS are unstable, fragmenting with the Au and the remnants of the sacrificial Ag core accumulating differently in various organs. We synthesized 43, 62, and 82 nm diameter HGNS through a galvanic replacement reaction, with nanoparticles of all sizes showing virtually identical NIR resonances at ∼800 nm. A theoretical model indicated that alloying, residual Ag in the nanoparticle core, nanoparticle porosity, and surface defects all contribute to the presence of the plasmon resonance at the observed wavelength, with the major contributing factor being the residual Ag. While PEG functionalization resulted in stable nanoparticles under laser irradiation in solution, an anomalous, strongly element-specific biodistribution observed in tumor-bearing mice suggests that an avid fragmentation of all three sizes of nanoparticles occurred in vivo. Stability studies across a wide range of pH environments and in serum confirmed HGNS fragmentation. These results show that NIR resonant HGNS contain residual Ag, which does not stay contained within the HGNS in vivo. This demonstrates the importance of tracking both materials of a galvanic replacement nanoparticle in biodistribution studies and of performing thorough nanoparticle stability studies prior to any intended in vivo trial application.
PMCID: PMC4004326  PMID: 24547810
plasmon; fragmentation; serum; near-infrared; photothermal therapy; nanomedicine; cancer
19.  Properties of plasmonic arrays produced by pulsed-laser nanostructuring of thin Au films 
A brief description of research advances in the area of short-pulse-laser nanostructuring of thin Au films is followed by examples of experimental data and a discussion of our results on the characterization of structural and optical properties of gold nanostructures. These consist of partially spherical or spheroidal nanoparticles (NPs) which have a size distribution (80 ± 42 nm) and self-organization characterized by a short-distance order (length scale ≈140 nm). For the NP shapes produced, an observably broader tuning range (of about 150 nm) of the surface plasmon resonance (SPR) band is obtained by renewal thin film deposition and laser annealing of the NP array. Despite the broadened SPR bands, which indicate damping confirmed by short dephasing times not exceeding 4 fs, the self-organized Au NP structures reveal quite a strong enhancement of the optical signal. This was consistent with the near-field modeling and micro-Raman measurements as well as a test of the electrochemical sensing capability.
PMCID: PMC4273299  PMID: 25551038
Au nanostructures; laser dewetting; laser nanostructuring; plasmonic enhancement; self-organization
20.  Rapid control of phase growth by nanoparticles 
Nature Communications  2014;5:3879.
Effective control of phase growth under harsh conditions (such as high temperature, highly conductive liquids or high growth rate), where surfactants are unstable or ineffective, is still a long-standing challenge. Here we show a general approach for rapid control of diffusional growth through nanoparticle self-assembly on the fast-growing phase during cooling. After phase nucleation, the nanoparticles spontaneously assemble, within a few milliseconds, as a thin coating on the growing phase to block/limit diffusion, resulting in a uniformly dispersed phase orders of magnitude smaller than samples without nanoparticles. The effectiveness of this approach is demonstrated in both inorganic (immiscible alloy and eutectic alloy) and organic materials. Our approach overcomes the microstructure refinement limit set by the fast phase growth during cooling and breaks the inherent limitations of surfactants for growth control. Considering the growing availability of numerous types and sizes of nanoparticles, the nanoparticle-enabled growth control will find broad applications.
Refining microstructure is an important goal in many material systems. Here, the authors report an approach for microstructure refinement based on nanoparticle self-assembling on a growing phase, which is shown to be effective for both metallic and organic systems.
PMCID: PMC4024764  PMID: 24809454
21.  Direct-writing of PbS nanoparticles inside transparent porous silica monoliths using pulsed femtosecond laser irradiation 
Nanoscale Research Letters  2011;6(1):542.
Pulsed femtosecond laser irradiation at low repetition rate, without any annealing, has been used to localize the growth of PbS nanoparticles, for the first time, inside a transparent porous silica matrix prepared by a sol-gel route. Before the irradiation, the porous silica host has been soaked within a solution containing PbS precursors. The effect of the incident laser power on the particle size was studied. X-ray diffraction was used to identify the PbS crystallites inside the irradiated areas and to estimate the average particle size. The localized laser irradiation led to PbS crystallite size ranging between 4 and 8 nm, depending on the incident femtosecond laser power. The optical properties of the obtained PbS-silica nanocomposites have been investigated using absorption and photoluminescence spectroscopies. Finally, the stability of PbS nanoparticles embedded inside the host matrices has been followed as a function of time, and it has been shown that this stability depends on the nanoparticle mean size.
PMCID: PMC3224756  PMID: 21970510
22.  Laser-Induced, Polarization Dependent Shape Transformation of Au/Ag Nanoparticles in Glass 
Nanoscale Research Letters  2009;4(11):1380-1383.
Bimetallic, initially spherical Ag/Au nanoparticles in glass prepared by ion implantation have been irradiated with intense femtosecond laser pulses at intensities still below the damage threshold of the material surface. This high-intensity laser processing produces dichroism in the irradiated region, which can be assigned to the observed anisotropic nanoparticle shapes with preferential orientation of the longer particle axis along the direction of laser polarization. In addition, the particle sizes have considerably been increased upon processing.
PMCID: PMC2893753  PMID: 20628450
Alloy nanoparticles; Glass; Laser irradiation; Femtosecond laser processing; Dichroism
23.  Laser-Induced, Polarization Dependent Shape Transformation of Au/Ag Nanoparticles in Glass 
Nanoscale Research Letters  2009;4(11):1380-1383.
Bimetallic, initially spherical Ag/Au nanoparticles in glass prepared by ion implantation have been irradiated with intense femtosecond laser pulses at intensities still below the damage threshold of the material surface. This high-intensity laser processing produces dichroism in the irradiated region, which can be assigned to the observed anisotropic nanoparticle shapes with preferential orientation of the longer particle axis along the direction of laser polarization. In addition, the particle sizes have considerably been increased upon processing.
PMCID: PMC2893753  PMID: 20628450
Alloy nanoparticles; Glass; Laser irradiation; Femtosecond laser processing; Dichroism
24.  Bio-functionalized dense-silica nanoparticles for MR/NIRF imaging of CD146 in gastric cancer 
Nano dense-silica (dSiO2) has many advantages such as adjustable core–shell structure, multiple drug delivery, and controllable release behavior. Improving the gastric tumor-specific targeting efficiency based on the development of various strategies is crucial for anti-cancer drug delivery systems.
Superparamagnetic iron oxide nanoparticles (SPION) were coated with dSiO2 as core–shell nanoparticles, and labeled with near infra-red fluorescence (NIRF) dye 800ZW (excitation wavelength: 778 nm/emission wavelength: 806 nm) and anti-CD146 monoclonal antibody YY146 for magnetic resonance (MR)/NIRF imaging study in xenograft gastric cancer model. The morphology and the size of pre- and postlabeling SPION@dSiO2 core–shell nanoparticles were characterized using transmission electron microscopy. Iron content in SPION@dSiO2 nanoparticles was measured by inductively coupled plasma optical emission spectrometry. Fluorescence microscopy and fluorescence-activated cell sorter studies were carried out to confirm the binding specificity of YY146 and 800ZW–SPION@dSiO2–YY146 on MKN45 cells. In vivo and in vitro NIRF imaging, control (nanoparticles only) and blocking studies, and histology were executed on MKN45 tumor-bearing nude mice to estimate the affinity of 800ZW–SPION@dSiO2–YY146 to target tumor CD146.
800ZW–SPION@dSiO2–YY146 nanoparticles were uniformly spherical in shape and dispersed evenly in a cell culture medium. The diameter of the nanoparticle was 20–30 nm with 15 nm SPION core and ~10 nm SiO2 shell, and the final concentration was 1.7 nmol/mL. Transverse relaxivity of SPION@dSiO2 dispersed in water was measured to be 110.57 mM−1·s−1. Fluorescence activated cell sorter analysis of the nanoparticles in MKN45 cells showed 14-fold binding of 800ZW–SPION@dSiO2–YY146 more than the control group 800ZW–SPION@dSiO2. Series of NIRF imaging post intravenous injection of 800ZW–SPION@dSiO2–YY146 demonstrated that the MKN45 xenograft tumor model could be clearly identified as early as a time point of 30 minutes postinjection. Quantitative analysis revealed that the tumor uptake peaked at 24 hours postinjection.
This is the first successful study of functional nanoparticles for MR/NIRF imaging of cell surface glycoprotein CD146 in gastric cancer model. Our results suggest that 800ZW–SPION@dSiO2–YY146 nanoparticles will be applicable in tumor for image-guided therapy/surgery.
PMCID: PMC4309778  PMID: 25653520
SPION; nanotechnology; EMT; SPION@dSiO2; xenograft; gastric cancer
25.  Synthesis of Silver Nanoparticles Using Hydroxyl Functionalized Ionic Liquids and Their Antimicrobial Activity 
We report a new one phase method for the synthesis of uniform monodisperse crystalline Ag nanoparticles in aqueous systems that has been developed by using newly synthesized mono and dihydroxylated ionic liquids and cationic surfactants based on 1,3-disubstituted imidazolium cations and halogens anions. The hydroxyl functionalized ionic liquids (HFILs) and hydroxyl functionalized cationic surfactants (HFCSs) also simultaneously acts both as the reductant and protective agent. By changing the carbon chain length, alcohol structure and anion of the 1,3-imidazolium based HFILs and HFCSs the particle size, uniform and dispersibility of nanoparticles in aqueous solvents could be controlled. Transmission electron microscopy (TEM), electron diffraction, UV-Vis and NMR, were used for characterization of HFILs, HFCSs and silver nanoparticles. TEM studies on the solution showed representative spherical silver nanoparticles with average sizes 2–8 nm, particularly 2.2 nm and 4.5 nm in size range and reasonable narrow particle size distributions (SD-standard distribution) 0.2 nm and 0.5 nm respectively. The all metal nanoparticles are single crystals with face centered cubic (fcc) structure. The silver nanoparticles surface of plasmon resonance band (λmax) around 420 nm broadened and little moved to the long wavelength region that indicating the formation of silver nanoparticles dispersion with broad absorption around infrared (IR) region. Silver complexes of these HFILs as well as different silver nanoparticles dispersions have been tested in vitro against several gram positive and gram negative bacteria and fungus. The silver nanoparticles providing environmentally friendly and high antimicrobial activity agents.
PMCID: PMC2635708  PMID: 19325785
Silver nanoparticles; hydroxyl functionalized ionic liquids; hydroxyl functionalized cationic surfactants; antimicrobial activity

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