On‐Chip Fabrication of Paclitaxel‐Loaded Chitosan Nanoparticles for Cancer Therapeutics

The use of solvent‐free microfluidics to fine‐tune the physical and chemical properties of chitosan nanoparticles for drug delivery is demonstrated. Nanoparticle self‐assembly is driven by pH changes in a water environment, which increases biocompatibility by avoiding organic solvent contamination common with traditional techniques. Controlling the time of mixing (2.5–75 ms) during nanoparticle self‐assembly enables us to adjust nanoparticle size and surface potential in order to maximize cellular uptake, which in turn dramatically increases drug effectiveness. The compact nanostructure of these nanoparticles preserves drug potency better than previous nanoparticles, and is more stable during long‐term circulation at physiological pH. However, when the nanoparticles encounter a tumor cell and the associated drop in pH, the drug contents are released. Moreover, the loading efficiency of hydrophobic drugs into the nanoparticles increases significantly from previous work to over 95%. The microfluidic techniques used here have applications not just for drug‐carrying nanoparticle fabrication, but also for the better control of virtually any self‐assembly process.     

A Multiparameter pH‐Sensitive Nanodevice Based on Plasmonic Nanopores

With controllable mass transfer and special optical properties, plasmonic nanopores may be applied as a nanodevice and possibly create a new generation of single molecule detection technique based on plasmon‐enhanced spectra. In the present study, gold nanoparticles self‐assemble into a gold porous sphere (GPS) on the tip of a glass nanopipette with the help of i‐motif DNA thiolated by both ends as linker molecules. The gaps among neighboring gold nanoparticles are considered as plasmonic nanopores. The size of the formed nanopores can be tuned by the folded–unfolded conformational change of i‐motif DNA upon pH adjustment from 4.5 to 7.0. Based on its tunable structural property, the GPS shows reversible changes in ionic current, potential, and surface‐enhanced Raman scattering signal. The GPS is further used to probe regional pH in single cells. The successful application of GPS in multiparameter pH probing and single cell analysis suggests that the new physical properties of the self‐assembled plasmonic nanopores can be used for fabricating multiple types of nanodevices and nanosensors.     

Highly Aligned Plasmonic Gold Nanorods in a DNA Matrix

Since the Lycurgus Cup was made in the 4th century, metal nanoparticles have attracted much interest due to the characteristics of the plasmonic and metamaterials that show beautiful colors. Despite these fascinating properties, the practical use is limited because it is difficult to control the orientation of the plasmonic nanoparticles. Here, highly aligned plasmonic gold nanorods are obtained using self‐assembled DNA material. Simple mechanical shearing results in long‐range DNA–gold nanorod arrays which show parallel, perpendicular, and zigzag configurations due to the competition between the shear force and DNA elasticity. The resulting surface plasmonic resonance properties of the aligned DNA–gold nanorods film show highly polarization‐dependent behavior in a large area, which is critical for optical and photonic applications. This simple way to form anisotropic plasmonic films can be used for plasmonic nanoparticles in potential applications such as displays and sensors.     

Assembly of Gold Nanoparticles in a Rod‐Like Fashion Using Proteins as Templates

An area of considerable current interest is the development of a practical approach for assembling inorganic nanoparticles into well‐defined arrays because such a technique would offer immense opportunities leading to applications in microimaging, optoelectronics, therapeutics, etc. This paper illustrates a new, simple one‐step process in which proteins act as templates to assemble gold nanoparticles in a shape‐selective fashion. We show, for the first time, that antibodies to vascular endothelial growth factor 165 isoform, 2C3, and epidermal growth factor receptor can act as templates when present in solution during the synthesis of gold nanoparticles. These proteins direct the assembly of the gold nanoparticles into rod‐like shapes when cooled to –20 °C followed by thawing at room temperature. Immunoglobulin G and bovine serum albumin can also direct the assembly process in a similar fashion; however, small molecules, such as poly(L ‐lysine) and lysine, cannot. The formation of a self‐assembled structure in the form of a continuous rod, or the assembly of discrete nanoparticles in a rod‐like fashion, can be tailored by controlling the ratio of the precursor gold salt, HAuCl₄, to the antibody/protein used as the template. The nanoconjugates are characterized using UV‐vis spectroscopy, transmission electron microscopy, and infrared spectroscopy. The nano‐bioconjugates obtained via this process may find wide application in areas ranging from optoelectronics and biosensors to therapeutics in neoplastic disorders.     

Protein/Polymer‐Based Dual‐Responsive Gold Nanoparticles with pH‐Dependent Thermal Sensitivity

This article presents the synthesis and physicochemical behavior of dual‐responsive plasmonic nanoparticles with reversible optical properties based on protein‐coated gold nanoparticles grafted with thermosensitive polymer brushes by means of surface‐initiated atom transfer radical polymerization (SI‐ATRP) that exhibit pH‐dependent thermo‐responsive behavior. Spherical gold NPs of two different sizes (15 nm and 60 nm) and with different stabilizing agents (citrate and cetyltrimethylammonium bromide (CTAB), respectively) were first capped with bovine serum albumin (BSA). The resulting BSA‐capped NPs (Au@BSA NPs) exhibited not only extremely high colloidal stability under physiological conditions, but also a reversible U‐shaped pH‐responsive behavior, similar to pure BSA. The ?‐amine of the L‐lysine in the protein coating was then used to covalently bind an ATRP‐initiator, allowing for the SI‐ATRP of thermosensitive polymer brushes of oligo(ethylene glycol) methacrylates with an LCST of 42 °C in pure water and around 37 °C under physiological conditions. Such protein coated nanoparticles grafted with thermosensitive polymers exhibit a smart pH‐dependent thermosensitive behavior.     

Biochemical Synthesis and Manipulation of a 70 nm DNA Linker for the Assembly of DNA‐Functionalized Gold Nanoparticles

DNA oligonucleotides are extraordinarily well suited as linkers for the programmable assembly of nanoparticles. To extend the scope of DNA‐directed particle assembly, a 70 nm DNA linker molecule for the DNA‐directed assembly of gold nanoparticles is synthesized by biochemical reactions. In particular, polymerase chain reaction (PCR) and subsequent restriction and ligation reactions are employed to synthesize the DNA linker, comprising a 178 base pair (bp) double helical core region supplemented with two sticky‐end binding sites of 12 nucleotides in length, attached to one of the core‐forming strands. The linker is used for the assembly of DNA‐functionalized gold nanoparticles employing yet another biochemical reaction, namely covalent linkage through the enzyme DNA ligase. The resulting nanoparticle assemblies are characterized by using atomic force microscopy. The methodology described here represents a general way of synthesizing programmable DNA linker molecules with dimensions that exceed those presently available by using chemical synthetic methods, and thus, supplements the synthetic toolbox of nanobiotechnology to asses complex and functional nanoparticle/linker architectures for potential applications in sensing and materials science.     

Nanoparticle‐enhanced light trapping in thin‐film silicon solar cells

A systematic investigation of the nanoparticle‐enhanced light trapping in thin‐film silicon solar cells is reported. The nanoparticles are fabricated by annealing a thin Ag film on the cell surface. An optimisation roadmap for the plasmon‐enhanced light‐trapping scheme for self‐assembled Ag metal nanoparticles is presented, including a comparison of rear‐located and front‐located nanoparticles, an optimisation of the precursor Ag film thickness, an investigation on different conditions of the nanoparticle dielectric environment and a combination of nanoparticles with other supplementary back‐surface reflectors. Significant photocurrent enhancements have been achieved because of high scattering and coupling efficiency of the Ag nanoparticles into the silicon device. For the optimum light‐trapping scheme, a short‐circuit current enhancement of 27% due to Ag nanoparticles is achieved, increasing to 44% for a “nanoparticle/magnesium fluoride/diffuse paint” back‐surface reflector structure. This is 6% higher compared with our previously reported plasmonic short‐circuit current enhancement of 38%. Copyright © 2011 John Wiley & Sons, Ltd.     

Three‐Dimensional Inkjet‐Printed Interconnects using Functional Metallic Nanoparticle Inks

Inkjet‐printed gold nanoparticle pillars are investigated as a high‐performance alternative to conventional flip‐chip interconnects for electronic packages, with significant advantages in terms of mechanical/chemical robustness and conductivity. The process parameters critical to pillar fabrication are described and highly uniform pillar arrays are demonstrated. More generally, this work underscores the impact of sintering on the electrical, mechanical, structural, and compositional properties of three‐dimensional nanoparticle‐based structures. Using heat treatments as low as 200 °C, electrical and mechanical performance that outcompetes conventional lead‐tin eutectic solder materials is achieved. With sintering conditions reaching 300 °C it is possible to achieve pillars with properties comparable to bulk gold. This work demonstrates the immense potential for both inkjet printing and metal nanoparticles to become a viable and cost‐saving alternative to both conventional electronic packaging processes and application‐specific integration schemes.     

Solvent‐Mediated Plasmon Tuning in a Gold‐Nanoparticle–Poly(Ionic Liquid) Composite

The design, synthesis, and characterization of a hierarchically ordered composite whose structure and optical properties can be reversibly switched by adjustment of solvent conditions are described. Solvent‐induced swelling and de‐swelling is shown to provide control over the internal packing arrangement and hence, optical properties of in situ synthesized metal nanoparticles. Specifically, a gold‐nanoparticle‐containing ionic‐liquid‐derived polymer is synthesized in a single step by UV irradiation of a metal‐ion‐precursor‐doped, self‐assembled ionic liquid gel, 1‐decyl‐3‐vinylimidazolium chloride. Small‐angle X‐ray scattering (SAXS) studies indicate that in the de‐swollen state, the freestanding polymer adopts a perforated lamellar structure. Optical spectroscopy of the dried composite reveals plasmon resonances positioned in the near‐IR. Strong particle–particle interactions arise from matrix‐promoted formation of aggregated 1D clusters or chains of gold nanoparticles. Upon swelling in alcohol, the composite undergoes a structural conversion to a disordered structure, which is accompanied by a color change from purple to pale pink and a shift in the surface plasmon resonance to 527 nm, consistent with isolated, non‐interacting particles. These results demonstrate the far‐field tuning of the plasmonic spectrum of gold nanoparticles by solvent‐mediated changes in its encapsulating matrix, offering a straightforward, low‐cost strategy for the fabrication of nanophotonic materials.     

基于介电泳机理的金纳米颗粒传感器装配方法

研究了一种基于介电泳机理的金纳米颗粒传感器装配方法。在分析介电泳工作原理的基础上,利用Comsol Multiphysics仿真软件,对平面微电极条件下所产生的空间电场进行了建模仿真,研究了金纳米粒子极化模型及相关介电泳频谱特性。设计加工了基于光刻标准工艺和引线键合技术的平面微电极阵列,构建了具有三维位移平台和视频监控装置的介电泳装配实验平台。以250nm金颗粒为实验对象,在理论分析基础上,完成了在微电极阵列上的介电泳组装实验研究,并通过电特性测量验证了组装结果。实验结果表明:金纳米颗粒的介电泳组装效果与介质溶液的电导率、电场频率和幅度、金纳米粒子浓度、电极间隙及作用时间有关,在适宜的条件下,采用介电泳技术可实现对金纳米颗粒的有效操控和纳米器件装配,该方法为纳米传感器的制造提供了一种有效途径。     

Spatial Analysis of Metal–PLGA Hybrid Microstructures Using 3D SERS Imaging

The incorporation of gold nanoparticles in biodegradable polymeric nanostructures with controlled shape and size is of interest toward different applications in nanomedicine. Properties of the polymer such as drug loading and antibody functionalization can be combined with the plasmonic properties of gold nanoparticles, to yield advanced hybrid materials. This study presents a new way to synthesize multicompartmental microgels, fibers, or cylinders, with embedded anisotropic gold nanoparticles. Gold nanoparticles dispersed in an organic solvent can be embedded within the poly(lactic‐co‐glycolic acid) (PLGA) matrix of polymeric microstructures, when prepared via electrohydrodynamic co‐jetting. Prior functionalization of the plasmonic nanoparticles with Raman active molecules allows for imaging of the nanocomposites by surface‐enhanced Raman scattering (SERS) microscopy, thereby revealing nanoparticle distribution and photostability. These exceptionally stable hybrid materials, when used in combination with 3D SERS microscopy, offer new opportunities for bioimaging, in particular when long‐term monitoring is required.     

DNA Origami‐Guided Assembly of the Roundest 60–100 nm Gold Nanospheres into Plasmonic Metamolecules

DNA origami can provide programmed information to guide the self‐assembly of gold nanospheres (Au NSs) into higher‐order supracolloids. Molecularly precise and truly 2D/3D integration of Au NSs is possible using DNA origami‐enabled assembly, and the resulting assemblies have potential applications in plasmonics and metamaterials. However, the relatively small size (<60 nm) and randomly faceted Au NSs that have been used thus far in DNA origami‐enabled assembly have limited their nanophotonic applications. Here, the robust self‐assembly of the 60–100 nm roundest Au NSs into metamolecular assemblies using 3D DNA origami is described. These Au NSs are successfully conjugated with DNA oligonucleotides and are therefore stable at high salt concentrations even without backfilling using organic ligands. The roundest Au NSs are successfully assembled into supracolloidal metamolecules and chains via 3D DNA origami. These plasmonic metamolecules and chains display strong electric and unnatural magnetic resonances that can be deterministically controlled.     

Electrically Oscillating Plasmonic Nanoparticles for Enhanced DNA Vaccination against Hepatitis C Virus

The promise of DNA vaccines is far‐reaching. However, the development of potent immunization methods remains a key challenge for its use in clinical applications. Here, an approach for in vivo DNA vaccination by electrically activated plasmonic Au nanoparticles is reported. The electrical excitation of plasmonic nanoparticles can drive vibrational and dipole‐like oscillations that are able to disrupt nearby cell membranes. In combination with their intrinsic ability to focus and magnify the electric field on the surface of cells, Au nanoparticles allow enhanced cell poration and facilitate the uptake of DNA vaccine. Mice immunized with this approach showed up to 100‐fold higher gene expression compared to control treatments (without nanoparticles) and exhibited significantly increased levels of both antibody and cellular immune responses against a model hepatitis C virus DNA vaccine. This approach can be tuned to establish controlled and targeted delivery of different types of therapeutic molecules into cells and live animals as well.     

Hierarchical Structuring in Block Copolymer Nanocomposites through Two Phase‐Separation Processes Operating on Different Time Scales

Tailoring the size and surface chemistry of nanoparticles allows one to control their position in a block copolymer, but this is usually limited to one‐dimensional distribution across domains. Here, the hierarchical assembly of poly(ethylene oxide)‐stabilized gold nanoparticles (Au‐PEO) into hexagonally packed clusters inside mesostructured ultrathin films of polystyrene‐block‐poly(methyl methacrylate) (PS‐b‐PMMA) is described. A close examination of the structural evolution at different nanoparticle filling fractions and PEO ligand molecular weights suggests that the mechanism leading to this structure‐within‐structure is the existence of two phase separation processes operating on different time scales. The length of the PEO ligand is shown to influence not only the interparticle distances but also the phase separation processes. These conclusions are supported by novel mesoscopic simulations, which provide additional insight into the kinetic and thermodynamic factors that are responsible for this behavior.     

Electrically Conductive Thin Films Prepared from Layer‐by‐Layer Assembly of Graphite Platelets

Layer‐by‐layer (LBL) assembly of carbon nanoparticles for low electrical contact resistance thin film applications is demonstrated. The nanoparticles consist of irregularly shaped graphite platelets, with acrylamide/ββ‐methacryl‐oxyethyl‐trimethyl‐ammonium copolymer as the cationic binder. Nanoparticle zeta (ζζ) potential and thereby electrostatic interactions are varied by altering the pH of graphite suspension as well as that of the binder suspension. Film thickness as a function of zeta potential, immersion time, and the number of layers deposited is obtained using Monte Carlo simulation of the energy dispersive spectroscopy measurements. Multilayer film surface morphology is visualized via field‐emission scanning electron microscopy and atomic‐force microscopy. Thin film electrical properties are characterized using electrical contact resistance measurements. Graphite nanoparticles are found to self‐assemble onto gold substrates through two distinct yet overlapping mechanisms. The first mechanism is characterized by logarithmic carbon uptake with respect to the number of deposition cycles and slow clustering of nanoparticles on the gold surface. The second mechanism results from more rapid LBL nanoparticle assembly and is characterized by linear weight uptake with respect to the number of deposition cycles and a constant bilayer thickness of 15 to 21 nm. Thin‐film electrical contact resistance is found to be proportional to the thickness after equilibration of the bilayer structure. Measured values range from 1.6 mΩ cm^?2 at 173 nm to 3.5 mΩ cm^?2 at 276 nm. Coating volume resistivity is reduced when electrostatic interactions are enhanced during LBL assembly.     

High‐Temperature Large‐Scale Self‐Assembly of Highly Faceted Monocrystalline Au Metasurfaces

Localized surface plasmon resonance (LSPR) devices based on resonant metallic metasurfaces have shown disruptive potential for many applications including biosensing and photocatalysis. Despite significant progress, highly performing Au plasmonic nanotextures often suffer of suboptimal electric field enhancement, due to damping effects in multicrystalline domains. Fabricating well‐defined Au nanocrystals over large surfaces is very challenging, and usually requires time‐intensive multi‐step processes. Here, presented are first insights on the large‐scale self‐assembly of monocrystalline Au nano‐islands with tunable size and separation, and their application as efficient LSPR surfaces. Highly homogeneous centimeter‐sized Au metasurfaces are fabricated by one‐step deposition and in situ coalescence of hot nanoparticle aerosols into a discontinuous monolayer of highly faceted monocrystals. First insights on the mechanisms driving the high‐temperature synthesis of these highly faceted Au nanotextures are obtained by molecular dynamic and detailed experimental investigation of their growth kinetics. Notably, these metasurfaces demonstrat high‐quality and tunable LSPR, enabling the fabrication of highly performing optical gas molecule sensors detecting down to 3 × 10^?6 variations in refractive index at room temperature. It is believed that these findings provide a rapid, low‐cost nanofabrication tool for the engineering of highly homogenous Au metasurfaces for large‐scale LSPR devices with application ranging from ultrasensitive optical gas sensors to photocatalytic macroreactors.     

Enhanced Collective Magnetic Properties Induced by the Controlled Assembly of Iron Oxide Nanoparticles in Chains

1D assemblies of magnetic nanoparticles are of great potential for designing novel nanostructured materials with enhanced collective magnetic properties. In that challenging context, a new assembly strategy is presented to prepare chains of magnetic nanoparticles that are well‐defined in structure and in spatial arrangement. The 1D assembly of iron oxide nanoparticles onto a substrate is controlled using “click” chemistry under an external magnetic field. Co‐aligned single nanoparticle chains separated by regular distances can be obtained by this strategy. The intrinsic high uniaxial anisotropy results in a strong enhancement of magnetic collective properties in comparison to 2D monolayers or isolated nanoparticles. In contrast to the intensively studied bundle chains of nanoparticles, the finely tuned chain structure reported here allows evidencing a first order intrachain dipolar interaction and a second order interchain magnetic coupling. This study offers new insights into the collective magnetic properties of highly anisotropic particulate assemblies which have been investigated by combining superconducting quantum interference device magnetometry, magnetic force microscopy, and ferromagnetic resonance.     

Plasmonic Charge Transfers in Large-Scale Metallic and Colloidal Photonic Crystal Slabs

The challenges in plasmonic charge transfer on a large-scale and low losses are systematically investigated by optical designs using 1D-plasmonic lattice structures. These plasmonic lattices are used as couplers to guide the energy in an underneath sub-wavelength titanium dioxide layer, resulting in the photonic crystal slabs. So far, photodetection is possible at energy levels close to the semiconductor bandgap; however, with the observed hybrid plasmonic–photonic modes, other wavelengths over the broad solar spectrum can be easily accessed for energy harvesting. The photo-enhanced current is measured locally with simple two-point contact on the centimeter-squared nanostructure by applying a bias voltage. As lattice couplers, interference lithographically fabricated conventional gold grating provides an advantage in fabrication; this optical concept is extended for the first time toward colloidal self-assembled nanoparticle chains to make the charge injection accessible for large-scale at reasonable costs with possibilities of photodetection by electric field vectors both along and perpendicular to the grating lines. To discuss the bottleneck of unavoidable isolating ligand shell of nanoparticles in contrast to the directly contacted nanobars, polarization-dependent ultrafast characterizations are carried out to study the charge injection processes in femtosecond resolution.     

Nanogap Plasmonic Structures Fabricated by Switchable Capillary‐Force Driven Self‐Assembly for Localized Sensing of Anticancer Medicines with Microfluidic SERS

Nanogap plasmonic structures, which can strongly enhance electromagnetic fields, enable widespread applications in surface‐enhanced Raman spectroscopy (SERS) sensing. Although the directed self‐assembly strategy has been adopted for the fabrication of micro/nanostructures on open surfaces, fabrication of nanogap plasmonic structures on complex substrates or at designated locations still remains a grand challenge. Here, a switchable self‐assembly method is developed to manufacture 3D nanogap plasmonic structures by combining supercritical drying and capillary‐force driven self‐assembly (CFSA) of micropillars fabricated by laser printing. The polymer pillars can stay upright during solvent development via supercritical drying, and then can form the nanogap after metal coating and subsequent CFSA. Due to the excellent flexibility of this method, diverse patterned plasmonic nanogap structures can be fabricated on planar or nonplanar substrates for SERS. The measured SERS signals of different patterned nanogaps in fluidic environment show a maximum enhancement factor ≈8 × 10⁷. Such nanostructures in microchannels also allow localized sensing for anticancer drugs (doxorubicin). Resulting from the marriage of top‐down and self‐assembly techniques, this method provides a facile, effective, and controllable approach for creating nanogap enabled SERS devices in fluidic channels, and hence can advance applications in precision medicine.     

Magnetic (Hyper)Thermia or Photothermia? Progressive Comparison of Iron Oxide and Gold Nanoparticles Heating in Water,in Cells,and In Vivo

Magnetic hyperthermia (MHT) and photothermal therapy (PTT) are emergent state‐of‐the‐art modalities for thermal treatment of cancer. While their mechanisms of action have distinct physical bases, both approaches rely on nanoparticle‐mediated remote onset of thermotherapy. Yet, are the two heating techniques interchangeable? Here, the heating obtained either with MHT or with PTT is compared. The heating is assessed in distinct environments and involves a set of nanomaterials differing in shape (spheres, cubes, stars, shells, and rods) as well as in composition (maghemite, magnetite, cobalt ferrite, and gold). The nanoparticle's heating efficacy in an aqueous medium is first evaluated. Subsequently, the heating efficiency within the cellular environment, where intracellular processing markedly decreases MHT, is compared. Conversely, endosomal sequestration could have a positive effect on PTT. Finally, iron oxide nanocubes and gold nanostars are compared in MHT and PTT in vivo within the heterogeneous intratumoral environment. Overall, two distinct therapeutic approaches, related to high dosage allowing MHT and low dosage associated with PTT, are identified. It is also demonstrated that PTT mediated by magnetic nanoparticles has an efficacy that is comparable to that of plasmonic nanoparticles, but only at significant nanoparticle dosages. At low concentrations, only plasmonic nanoparticles can deliver a therapeutic heating.