Elsabahy, Mahmoud; Wooley, Karen L.
2014-01-01
Polymeric nanoparticles are promising delivery platforms for various biomedical applications. One of the main challenges toward the development of therapeutic nanoparticles is the premature disassembly and release of the encapsulated drug. Among the different strategies to enhance the kinetic stability of polymeric nanoparticles, shell- and core-crosslinking have been shown to provide robust character, while creating a suitable environment for encapsulation of a wide range of therapeutics, including hydrophilic, hydrophobic, metallic, and small and large biomolecules, with gating of their release as well. The versatility of shell- and core-crosslinked nanoparticles is driven from the ease by which the structures of the shell- and core-forming polymers and crosslinkers can be modified. In addition, postmodification with cell-recognition moieties, grafting of antibiofouling polymers, or chemical degradation of the core to yield nanocages allow the use of these robust nanostructures as “smart” nanocarriers. The building principles of these multifunctional nanoparticles borrow analogy from the synthesis, supramolecular assembly, stabilization, and dynamic activity of the naturally driven biological nanoparticles such as proteins, lipoproteins, and viruses. In this review, the chemistry involved during the buildup from small molecules to polymers to covalently stabilized nanoscopic objects is detailed, with contrast of the strategies of the supramolecular assembly of polymer building blocks followed by intramicellar stabilization into shell-, core-, or core–shell-crosslinked knedel-like nanoparticles versus polymerization of polymers into nanoscopic molecular brushes followed by further intramolecular covalent stabilization events. The rational design of shell-crosslinked knedel-like nanoparticles is then elaborated for therapeutic packaging and delivery, with emphasis on the polymer chemistry aspects to accomplish the synthesis of such nanoparticulate systems. PMID:25574072
Thermally Stable Gold Nanoparticles with a Crosslinked Diblock Copolymer Shell
NASA Astrophysics Data System (ADS)
Jang, Se Gyu; Khan, Anzar; Hawker, Craig J.; Kramer, Edward J.
2010-03-01
The use of polymer-coated Au nanoparticles prepared using oligomeric- or polymeric-ligands tethered by Au-S bonds for incorporation into block copolymer templates under thermal processing has been limited due to dissociation of the Au-S bond at T > 100^oC where compromises their colloidal stability. We report a simple route to prepare sub-5nm gold nanoparticles with a thermally stable polymeric shell. An end-functional thiol ligand consisting of poly(styrene-b-1,2&3,4-isoprene-SH) is synthesized by anionic polymerization. After a standard thiol ligand synthesis of Au nanoparticles, the inner PI block is cross-linked through reaction with 1,1,3,3-tetramethyldisiloxane. Gold nanoparticles with the cross-linked shell are stable in organic solvents at 160^oC as well as in block copolymer films of PS-b-P2VP annealed in vacuum at 170^oC for several days. These nanoparticles can be designed to strongly segregate to the PS-P2VP interface resulting in very large Au nanoparticle volume fractions φp without macrophase separation as well as transitions between lamellar and bicontinuous morphologies as φp increases.
Ibricevic, Aida; Guntsen, Sean P.; Zhang, Ke; Shrestha, Ritu; Liu, Yongjian; Sun, Jing Yi; Welch, Michael J.; Wooley, Karen L.; Brody, Steven L.
2013-01-01
The airway provides a direct route for administration of nanoparticles bearing therapeutic or diagnostic payloads to the lung, however optimization of nanoplatforms for intracellular delivery remains challenging. Poly(ethylene glycol) (PEG) surface modification improves systemic performance but less is known about PEGylated nanoparticles administered to the airway. To test this, we generated a library of cationic, shell crosslinked knedel-like nanoparticles (cSCKs), including PEG (1.5 kDa PEG; 2, 5, 10 molecules/polymer arm) on the outer shell. Delivery of PEGylated cSCK to the mouse airway showed significantly less inflammation in a PEG dose-dependent manner. PEGylation also enhanced the entry of cSCKs in lung alveolar epithelial cells and improved surfactant penetration. The PEGylation effect could be explained by the altered mechanism of endocytosis. While non-PEGylated cSCKs used the clathrin-dependent route for endocytosis, entry of PEGylated cSCK was clathrin-independent. Thus, nanoparticle surface modification with PEG represents an advantageous design for lung delivery. PMID:23453959
Formation mechanism of monodispersed spherical core-shell ceria/polymer hybrid nanoparticles
DOE Office of Scientific and Technical Information (OSTI.GOV)
Izu, Noriya, E-mail: n-izu@aist.go.jp; Uchida, Toshio; Matsubara, Ichiro
2011-08-15
Graphical abstract: The formation mechanism for core-shell nanoparticles is considered to be as follows: nucleation and particle growth occur simultaneously (left square); very slow particle growth occurs (middle square). Highlights: {yields} The size of the resultant nanoparticles was strongly and complicatedly dependent on the set temperature used during reflux heating and the PVP molecular weight. {yields} The size of the nanoparticles increased by a 2-step process as the reflux heating time increased. {yields} The IR spectral changes with increasing reflux time indicated the increase in the number of cross-linked polymers in the shell. -- Abstract: Very unique core-shell ceria (ceriummore » oxide)/polymer hybrid nanoparticles that have monodispersed spherical structures and are easily dispersed in water or alcohol without the need for a dispersant were reported recently. The formation mechanism of the unique nanoparticles, however, was not clear. In order to clarify the formation mechanism, these nanoparticles were prepared using a polyol method (reflux heating) under varied conditions of temperature, time, and concentration and molecular weight of added polymer (poly(vinylpyrrolidone)). The size of the resultant nanoparticles was strongly and complicatedly dependent on the set temperature used during reflux heating and the poly(vinylpyrrolidone) molecular weight. Furthermore, the size of the nanoparticles increased by a 2-step process as the reflux heating time increased. The IR spectral changes with increasing reflux time indicated the increase in the number of cross-linked polymers in the shell. From these results, the formation mechanism was discussed and proposed.« less
Hierarchically assembled theranostic nanostructures for siRNA delivery and imaging applications.
Shrestha, Ritu; Elsabahy, Mahmoud; Luehmann, Hannah; Samarajeewa, Sandani; Florez-Malaver, Stephanie; Lee, Nam S; Welch, Michael J; Liu, Yongjian; Wooley, Karen L
2012-10-24
Dual functional hierarchically assembled nanostructures, with two unique functions of carrying therapeutic cargo electrostatically and maintaining radiolabeled imaging agents covalently within separate component building blocks, have been developed via the supramolecular assembly of several spherical cationic shell cross-linked nanoparticles clustered around a central anionic shell cross-linked cylinder. The shells of the cationic nanoparticles and the hydrophobic core domain of the anionic central cylindrical nanostructure of the assemblies were utilized to complex negatively charged nucleic acids (siRNA) and to undergo radiolabeling, respectively, for potential theranostic applications. The assemblies exhibited exceptional cell transfection and radiolabeling efficiencies, providing an overall advantage over the individual components, which could each facilitate only one or the other of the functions.
Shell crosslinked nanoparticles carrying silver antimicrobials as therapeutics†
Li, Yali; Hindi, Khadijah; Watts, Kristin M.; Taylor, Jane B.; Zhang, Ke; Li, Zicheng
2010-01-01
Amphiphilic polymer nanoparticles loaded with silver cations or/and N-heterocyclic carbene–silver complexes were assessed as antimicrobial agents against Gram-negative pathogens Escherichia coli and Pseudomonas aeruginosa. PMID:20024313
NASA Astrophysics Data System (ADS)
Marchyk, Nataliya; Maximilien, Jacqueline; Beyazit, Selim; Haupt, Karsten; Sum Bui, Bernadette Tse
2014-02-01
A novel approach using one-pot synthesis for the production of uniform, iniferter-bound polystyrene core nanoparticles of size 30-40 nm is described. Conventional oil-in-water emulsion polymerisation of styrene and divinylbenzene, combining a hybrid initiation system (thermal and UV), triggered sequentially, was employed to form the surface-bound thiocarbamate iniferters in situ. The iniferter cores were then used as seeds for re-initiating further polymerisation by UV irradiation to produce water-compatible core-shell nanoparticles. Grafting of various shell-types is demonstrated: linear polymers of poly(N-isopropylacrylamide) brushes, crosslinked polymers bearing different surface charges and molecularly imprinted polymers. The shell thickness was readily tuned by varying the monomers' concentration and polymerisation time. Our method is straightforward and in addition, gives access to the preparation of fluorescent seeds and the possibility of grafting nanosized multiple shells. The core-shell nanoparticles were fully characterised by dynamic light scattering, transmission electron microscopy, Fourier transform infrared spectroscopy and microelemental analysis.A novel approach using one-pot synthesis for the production of uniform, iniferter-bound polystyrene core nanoparticles of size 30-40 nm is described. Conventional oil-in-water emulsion polymerisation of styrene and divinylbenzene, combining a hybrid initiation system (thermal and UV), triggered sequentially, was employed to form the surface-bound thiocarbamate iniferters in situ. The iniferter cores were then used as seeds for re-initiating further polymerisation by UV irradiation to produce water-compatible core-shell nanoparticles. Grafting of various shell-types is demonstrated: linear polymers of poly(N-isopropylacrylamide) brushes, crosslinked polymers bearing different surface charges and molecularly imprinted polymers. The shell thickness was readily tuned by varying the monomers' concentration and polymerisation time. Our method is straightforward and in addition, gives access to the preparation of fluorescent seeds and the possibility of grafting nanosized multiple shells. The core-shell nanoparticles were fully characterised by dynamic light scattering, transmission electron microscopy, Fourier transform infrared spectroscopy and microelemental analysis. Electronic supplementary information (ESI) available. See DOI: 10.1039/c3nr05295h
Shrestha, Ritu; Elsabahy, Mahmoud; Florez-Malaver, Stephanie; Samarajeewa, Sandani; Wooley, Karen L.
2012-01-01
Cationic shell crosslinked knedel-like nanoparticles (cSCKs) have emerged as a highly efficient transfection agent for nucleic acids delivery. In this study, a new class of cSCKs with tunable buffering capacities has been developed by altering the amounts of histamines and primary amines incorporated into their crosslinked shell regions. The effect of histamine content of these nanoparticles with a hydrodynamic diameter of ca. 20 nm, on the siRNA-binding affinity, cytotoxicity, immunogenicity, and transfection efficiency was investigated. The modification of cSCKs with histamine was found to reduce the siRNA-binding affinity and cellular binding. On the other hand, it significantly reduced the toxicity and immunogenicity of the nanoparticles with subsequent increase in the transfection efficiency. In addition, escape from endosomes was facilitated by having two species of low and high pKas (i.e. histamine and primary amine groups, respectively), as demonstrated by the potentiometric titration experiments and the effect of bafilomycin A1, an inhibitor of the endosomal acidification, on the transfection efficiency of cSCKs. Histamine modification of 15 mol% was a threshold, above which cSCKs with higher histamine content completely lost the ability to bind siRNA and to transfect cells. This study highlights the potential of histamine incorporation to augment the gene silencing activity of cationic nanoparticles, reduce their toxicity, and increase their biocompatibility, which is of particular importance in the design of nucleic acids delivery vectors. PMID:22901966
Atta, Ayman M; El-Mahdy, Gamal A; Al-Lohedan, Hamad A; El-Saeed, Ashraf M
2015-01-14
This work presents a new method to prepare poly(sodium acrylate) magnetite composite nanoparticles. Core/shell type magnetite nanocomposites were synthesized using sodium acrylate as monomer and N,N-methylenebisacrylamide (MBA) as crosslinker. Microemulsion polymerization was used for constructing core/shell structures with magnetite nanoparticles as core and poly(sodium acrylate) as shell. Fourier transform infrared spectroscopy (FTIR) was employed to characterize the nanocomposite chemical structure. Transmittance electron microscopy (TEM) was used to examine the morphology of the modified poly(sodium acrylate) magnetite composite nanoparticles. These particle will be evaluated for effective anticorrosion behavior as a hydrophobic surface on stainless steel. The composite nanoparticles has been designed by dispersing nanocomposites which act as a corrosion inhibitor. The inhibition effect of AA-Na/magnetite composites on steel corrosion in 1 M HCl solution was investigated using potentiodynamic polarization curves and electrochemical impedance spectroscopy (EIS). Polarization measurements indicated that the studied inhibitor acts as mixed type corrosion inhibitor. EIS spectra exhibit one capacitive loop. The different techniques confirmed that the inhibition efficiency reaches 99% at 50 ppm concentration. This study has led to a better understanding of active anticorrosive magnetite nanoparticles with embedded nanocomposites and the factors influencing their anticorrosion performance.
Enhanced Stability and Bioconjugation of Photo-cross-linked Polystyrene-Shell, Au-Core Nanoparticles
Chen, Ying; Cho, Juhee; Young, Alexi; Taton, T. Andrew
2008-01-01
Encapsulating Au nanoparticles within a shell of photo-cross-linked block copolymer surfactant dramatically improves the physical and chemical stability of the nanoparticles, particularly when they are applied as bioconjugates. Photo-cross-linkable block copolymer amphiphiles [polystyrene-co-poly(4-vinyl benzophenone)]-block-poly(acrylic acid) [(PS-co-PVBP)-b-PAA] and [poly(styrene)-co-poly(4-vinyl benzophenone)]-block-poly(ethylene oxide) [(PS-co-PVBP)-b-PEO] were assembled around Au nanoparticles ranging from 12 nm to 108 nm in diameter. UV irradiation cross-linked the PVBP groups on the polymer to yield particles that withstood extremes of temperature, ionic strength, and chemical etching. Streptavidin was attached to [PS-co-PVBP]-b-PAA coated particles using the same noncovalent and covalent conjugation protocols used to bind biomolecules to divinylbenzene-crosslinked polystyrene microspheres. We expect that these particles will be useful as plasmonic, highly light-scattering and light-absorbing analogs to fluorescently labeled polystyrene nanospheres. PMID:17530871
Photo-crosslinked hyaluronic acid coated upconverting nanoparticles
NASA Astrophysics Data System (ADS)
Mrazek, Jiri; Kettou, Sofiane; Matuska, Vit; Svozil, Vit; Huerta-Angeles, Gloria; Pospisilova, Martina; Nesporova, Kristina; Velebny, Vladimir
2017-02-01
Hyaluronic acid (HA)-coated inorganic nanoparticles display enhanced interaction with the CD44 receptors which are overexpressed in many types of cancer cells. Here, we describe a modification of core-shell β-NaY0.80Yb0.18Er0.02F4@NaYF4 nanoparticles (UCNP) by HA derivative bearing photo-reactive groups. UCNP capped with oleic acid were firstly transferred to aqueous phase by an improved protocol using hydrochloric acid or lactic acid treatment. Subsequently, HA bearing furanacryloyl moieties (HA-FU) was adsorbed on the nanoparticle surface and crosslinked by UV irradiation. The crosslinking resulted in stable HA coating, and no polymer desorption was observed. As-prepared UCNP@HA-FU show a hydrodynamic diameter of about 180 nm and are colloidally stable in water and cell culture media. The cellular uptake by normal human fibroblasts and MDA MB-231 cancer cell line was investigated by upconversion luminescence imaging.
NASA Astrophysics Data System (ADS)
Zhang, Y.; Jin, Q.; Chen, Y.; Zhao, J.
2011-10-01
Taking advantage of the specific hydrogen bonding interactions, stable and pH-responsive core-shell nanoparticles based on hydroxyethyl cellulose (HEC) and polymethacrylic acid (PMAA) networks, with a < D h > size ranging from 190 to 250 nm, can be efficiently prepared via facile one-step co-polymerization of methacrylic acid (MAA) and N, N'-methylenebisacrylamide (MBA) on HEC template in water. Using dynamic light scattering, electrophoretic light scattering, fluorescence spectrometry, thermo-gravimetric analysis, TEM, and AFM observations, the influence of crosslinker MBA as well as the reaction parameters were studied. The results show that after the introduction of crosslinker MBA, the nanoparticles became less compact; their size exhibited a smaller pH sensitivity, and their stability against pH value was improved greatly. Furthermore, the size, structure, and pH response of the nanoparticles can be adjusted via varying the reaction parameters: nanoparticles of smaller size, more compact structure, and higher swelling capacity were produced as pH value of the reaction medium increased or the HEC/MAA ratio decreased; while nanoparticles of smaller size, less compact structure and smaller swelling capacity were produced as the total feeding concentration increased.
Hybrid Core-Shell (HyCoS) Nanoparticles produced by Complex Coacervation for Multimodal Applications
NASA Astrophysics Data System (ADS)
Vecchione, D.; Grimaldi, A. M.; Forte, E.; Bevilacqua, Paolo; Netti, P. A.; Torino, E.
2017-03-01
Multimodal imaging probes can provide diagnostic information combining different imaging modalities. Nanoparticles (NPs) can contain two or more imaging tracers that allow several diagnostic techniques to be used simultaneously. In this work, a complex coacervation process to produce core-shell completely biocompatible polymeric nanoparticles (HyCoS) for multimodal imaging applications is described. Innovations on the traditional coacervation process are found in the control of the reaction temperature, allowing a speeding up of the reaction itself, and the production of a double-crosslinked system to improve the stability of the nanostructures in the presence of a clinically relevant contrast agent for MRI (Gd-DTPA). Through the control of the crosslinking behavior, an increase up to 6 times of the relaxometric properties of the Gd-DTPA is achieved. Furthermore, HyCoS can be loaded with a high amount of dye such as ATTO 633 or conjugated with a model dye such as FITC for in vivo optical imaging. The results show stable core-shell polymeric nanoparticles that can be used both for MRI and for optical applications allowing detection free from harmful radiation. Additionally, preliminary results about the possibility to trigger the release of a drug through a pH effect are reported.
2014-01-01
The use of nebulizable, nanoparticle-based antimicrobial delivery systems can improve efficacy and reduce toxicity for treatment of multi-drug-resistant bacteria in the chronically infected lungs of cystic fibrosis patients. Nanoparticle vehicles are particularly useful for applying broad-spectrum silver-based antimicrobials, for instance, to improve the residence time of small-molecule silver carbene complexes (SCCs) within the lung. Therefore, we have synthesized multifunctional, shell cross-linked knedel-like polymeric nanoparticles (SCK NPs) and capitalized on the ability to independently load the shell and core with silver-based antimicrobial agents. We formulated three silver-loaded variants of SCK NPs: shell-loaded with silver cations, core-loaded with SCC10, and combined loading of shell silver cations and core SCC10. All three formulations provided a sustained delivery of silver over the course of at least 2–4 days. The two SCK NP formulations with SCC10 loaded in the core each exhibited excellent antimicrobial activity and efficacy in vivo in a mouse model of Pseudomonas aeruginosa pneumonia. SCK NPs with shell silver cation-load only, while efficacious in vitro, failed to demonstrate efficacy in vivo. However, a single dose of core SCC10-loaded SCK NPs (0.74 ± 0.16 mg Ag) provided a 28% survival advantage over sham treatment, and administration of two doses (0.88 mg Ag) improved survival to 60%. In contrast, a total of 14.5 mg of Ag+ delivered over 5 doses at 12 h intervals was necessary to achieve a 60% survival advantage with a free-drug (SCC1) formulation. Thus, SCK NPs show promise for clinical impact by greatly reducing antimicrobial dosage and dosing frequency, which could minimize toxicity and improve patient adherence. PMID:23718195
Georgopanos, Prokopios; Schneider, Gerold A; Dreyer, Axel; Handge, Ulrich A; Filiz, Volkan; Feld, Artur; Yilmaz, Ezgi D; Krekeler, Tobias; Ritter, Martin; Weller, Horst; Abetz, Volker
2017-08-04
In this work the fabrication of hard, stiff and strong nanocomposites based on polybutadiene and iron oxide nanoparticles is presented. The nanocomposites are fabricated via a general concept for mechanically superior nanocomposites not based on the brick and mortar structure, thus on globular nanoparticles with nanosized organic shells. For the fabrication of the composites oleic acid functionalized iron oxide nanoparticles are decorated via ligand exchange with an α,ω-polybutadiene dicarboxylic acid. The functionalized particles were processed at 145 °C. Since polybutadiene contains double bonds the nanocomposites obtained a crosslinked structure which was enhanced by the presence of oxygen or sulfur. It was found that the crosslinking and filler percolation yields high elastic moduli of approximately 12-20 GPa and hardness of 15-18 GPa, although the polymer volume fraction is up to 40%. We attribute our results to a catalytically enhanced crosslinking reaction of the polymer chains induced by oxygen or sulfur and to the microstructure of the nanocomposite.
Sun, Jiao-Tong; Piao, Ji-Gang; Wang, Long-Hai; Javed, Mohsin; Hong, Chun-Yan; Pan, Cai-Yuan
2013-09-01
A versatile one-pot strategy for the preparation of reversibly cross-linked polymer-coated mesoporous silica nanoparticles (MSNs) via surface reversible addition-fragmentation chain transfer (RAFT) polymerization is presented for the first time in this paper. The less reactive monomer oligo(ethylene glycol) acrylate (OEGA) and the more reactive cross-linker N,N'-cystaminebismethacrylamide (CBMA) are chosen to be copolymerized on the external surfaces of RAFT agent-functionalized MSNs to form the cross-linked polymer shells. Owing to the reversible cleavage and restoration of disulfide bonds via reduction/oxidation reactions, the polymer shells can control the on/off switching of the nanopores and regulate the drug loading and release. The redox-responsive release of doxorubicin (DOX) from this drug carrier is realized. The protein adsorption, in vitro cytotoxicity assays, and endocytosis studies demonstrate that this biocompatible vehicle is a potential candidate for delivering drugs. It is expected that this versatile grafting strategy may help fabricate satisfying MSN-based drug delivery systems for clinical application. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Size-Tunable and Functional Core-Shell Structured Silica Nanoparticles for Drug Release
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chi, Fangli; Guo, Ya Nan; Liu, Jun
2010-02-18
Size-tunable silica cross-linked micellar core-shell nanoparticles (SCMCSNs) were successfully synthesized from a Pluronic nonionic surfactant (F127) template system with organic swelling agents such as 1,3,5-trimethylbenzene (TMB) and octanoic acid at room temperature. The size and morphology of SCMCSNs were directly evidenced by TEM imaging and DLS measurements (up to ~90 nm). Pyrene and coumarin 153 (C153) were used as fluorescent probe molecules to investigate the effect and location of swelling agent molecules. Papaverine as a model drug was used to measure the loading capacity and release property of nanoparticles. The swelling agents can enlarge the nanoparticle size and improve themore » drug loading capacity of nanoparticles. Moreover, the carboxylic acid group of fatty acid can adjust the release behavior of the nanoparticles.« less
Cationic Shell-crosslinked Knedel-like (cSCK) Nanoparticles for Highly Efficient PNA Delivery
Fang, Huafeng; Zhang, Ke; Shen, Gang; Wooley, Karen L.; Taylor, John-Stephen A.
2009-01-01
Peptide nucleic acids have a number of features that make them an ideal platform for the development of in vitro biological probes and tools. Unfortunately, their inability to pass through membranes has limited their in vivo application as diagnostic and therapeutic agents. Herein, we describe the development of cationic shell-crosslinked knedel-like (cSCK) nanoparticles as highly efficient vehicles for the delivery of PNAs into cells, either through electrostatic complexation with a PNA•ODN hybrid, or through a bioreductively cleavable disulfide linkage to a PNA. These delivery systems are better than the standard lipofectamine/ODN-mediated method and much better than the Arg9-mediated method for PNA delivery in HeLa cells, showing lower toxicity and higher bioactivity. The cSCKs were also found to facilitate both endocytosis and endosomal release of the PNAs, while themselves remaining trapped in the endosomes. PMID:19231840
NASA Astrophysics Data System (ADS)
Bravo-Osuna, Irene; Vauthier, Christine; Farabollini, Alessandra; Millotti, Gioconda; Ponchel, Gilles
2008-12-01
Surface modified nanoparticles composed of poly(isobutylcyanoacrylate) (PIBCA) cores surrounded by a chitosan and thiolated chitosan gel layer were prepared and characterized in previous works. The presence of such biopolymers on the nanoparticle surface conferred those nanosystems interesting characteristics that might partially overcome the gastrointestinal enzymatic barrier, improving the oral administration of pharmacologically active peptides. In the present work, the antiprotease behaviour of this family of core-shell nanoparticles was in vitro tested against two model metallopeptidases present in the gastrointestinal tract (GIT): Carboxypeptidase A -CP A- (luminal protease) and Leucine Aminopeptidase M -LAP M- (membrane protease). As previous step, the zinc-binding capacity of these nanoparticles was evaluated. Interestingly, an improvement of both the zinc-binding capacity and the antiprotease effect of chitosan was observed when the biopolymers (chitosan and thiolated chitosan) were used as coating component of the core-shell nanoparticles, in comparison with their behaviour in solution, thanks to the different biopolymer chains rearrangement. The presence of amino, hydroxyl and thiol groups on the nanoparticle surface promoted zinc binding and hence the inhibition of the metallopeptidases analysed. On the contrary, the occurrence of a cross-linked structure in the gel layer surrounding the PIBCA cores of thiolated formulations, due to the formation of interchain and intrachain disulphide bonds, partially limited the inhibition of the proteases. The low accessibility of cations to the active groups of the cross-linked polymeric shell was postulated as a possible explanation of this behaviour. Results obtained in this work make this family of surface-modified nanocarriers promising candidates for the successfull administration of pharmacologically active peptides and proteins by the oral route.
Packaging of DNA by shell crosslinked nanoparticles.
Thurmond, K B; Remsen, E E; Kowalewski, T; Wooley, K L
1999-07-15
We demonstrate compaction of DNA with nanoscale biomimetic constructs which are robust synthetic analogs of globular proteins. These constructs are approximately 15 nm in diameter, shell crosslinked knedel-like (SCKs) nanoparticles, which are prepared by covalent stabilization of amphiphilic di-block co-polymer micelles, self-assembled in an aqueous solution. This synthetic approach yields size-controlled nanoparticles of persistent shape and containing positively charged functional groups at and near the particle surface. Such properties allow SCKs to bind with DNA through electrostatic interactions and facilitate reduction of the DNA hydrodynamic diameter through reversible compaction. Compaction of DNA by SCKs was evident in dynamic light scattering experiments and was directly observed by in situ atomic force microscopy. Moreover, enzymatic digestion of the DNA plasmid (pBR322, 4361 bp) by Eco RI was inhibited at low SCK:DNA ratios and prevented when [le]60 DNA bp were bound per SCK. Digestion by Msp I in the presence of SCKs resulted in longer DNA fragments, indicating that not all enzyme cleavage sites were accessible within the DNA/SCK aggregates. These results have implications for the development of vehicles for successful gene therapy applications.
Zhu, Caiying; Xiao, Jingjing; Tang, Ming; Feng, Hua; Chen, Wulian; Du, Ming
2017-01-01
The preparation of polymer therapeutics capable of controlled release of multiple chemotherapeutic drugs has remained a tough problem in synergistic combination cancer therapy. Herein, a novel dual-drug co-delivery system carrying doxorubicin (DOX) and platinum(IV) (Pt[IV]) was developed. An amphiphilic diblock copolymer, PCL-b-P(OEGMA-co-AzPMA), was synthesized and used as a nanoscale drug carrier in which DOX and Pt(IV) could be packaged together. The copolymers were shell cross-linked by Pt(IV) prodrug via a click reaction. Studies on the in vitro drug release and cellular uptake of the dual-drug co-delivery system showed that the micelles were effectively taken up by the cells and simultaneously released drugs in the cells. Futhermore, the co-delivery polymer nanoparticles caused much higher cell death in HeLa and A357 tumor cells than either the free drugs or single-drug-loaded micelles at the same dosage, exhibiting a synergistic combination of DOX and Pt(IV). The results obtained with the shell cross-linked micelles based on an anticancer drug used as a cross-linking linkage suggested a promising application of the micelles for multidrug delivery in combination cancer therapy. PMID:28553108
NASA Astrophysics Data System (ADS)
Pankov, A. M.; Bredikhina, A. S.; Kulnitskiy, B. A.; Perezhogin, I. A.; Skryleva, E. A.; Parkhomenko, Yu. N.; Popov, M. Yu.; Blank, V. D.
2017-08-01
A pressure-induced phase transition of multiwall carbon nanotubes (MWNT) to a new structure at room temperature is studied using a shear diamond anvil cell, X-ray photoelectron spectra (XPS), transmission electron microscope (TEM) and Raman procedures. We observe a cardinal pressure-induced change in the nanoparticles shape from multi-shell tubes to multi-shell spheres. MWNT transforms to onions with layers cross-linked by sp3 bonds under the 45-65 GPa compressive stress combined with shear deformation at room temperature. TEM and XPS results show that about 40% of the carbon atoms in the new phase are sp3-bounded.
Silica passivated conjugated polymer nanoparticles for biological imaging applications
NASA Astrophysics Data System (ADS)
Bourke, Struan; Urbano, Laura; Olona, Antoni; Valderrama, Ferran; Dailey, Lea Ann; Green, Mark A.
2017-02-01
Colorectal and prostate cancers are major causes of cancer-related death, with early detection key to increased survival. However, as symptoms occur during advanced stages and current diagnostic methods have limitations, there is a need for new fluorescent probes that remain bright, are biocompatible and can be targeted. Conjugated polymer nanoparticles have shown great promise in biological imaging due to their unique optical properties. We have synthesised small, bright, photo-stable CN-PPV, nanoparticles encapsulated with poloxamer polymer and a thin silica shell. By incubating the CN-PPV silica shelled cross-linked (SSCL) nanoparticles in mammalian (HeLa) cells; we were able to show that cellular uptake occurred. Uptake was also shown by incubating the nanoparticles in RWPE-1, WPE1-NB26 and WPE1- NA22 prostate cancer cell lines. Finally, HEK cells were used to show the particles had limited cytotoxicity.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Ishige, Ryohei; Williams, Gregory A.; Higaki, Yuji
A molded film of single-component polymer-grafted nanoparticles (SPNP), consisting of a spherical silica core and densely grafted polymer chains bearing hydrogen-bonding side groups capable of physical crosslinking, was investigated byin situultra-small-angle X-ray scattering (USAXS) measurement during a uniaxial stretching process. Static USAXS revealed that the molded SPNP formed a highly oriented twinned face-centered cubic (f.c.c.) lattice structure with the [11-1] plane aligned nearly parallel to the film surface in the initial state. Structural analysis ofin situUSAXS using a model of uniaxial deformation induced by rearrangement of the nanoparticles revealed that the f.c.c. lattice was distorted in the stretching direction inmore » proportion to the macroscopic strain until the strain reached 35%, and subsequently changed into other f.c.c. lattices with different orientations. The lattice distortion and structural transition behavior corresponded well to the elastic and plastic deformation regimes, respectively, observed in the stress–strain curve. The attractive interaction of the hydrogen bond is considered to form only at the top surface of the shell and then plays an effective role in cross-linking between nanoparticles. The rearrangement mechanism of the nanoparticles is well accounted for by a strong repulsive interaction between the densely grafted polymer shells of neighboring particles.« less
Ishige, Ryohei; Williams, Gregory A.; Higaki, Yuji; ...
2016-04-19
A molded film of single-component polymer-grafted nanoparticles (SPNP), consisting of a spherical silica core and densely grafted polymer chains bearing hydrogen-bonding side groups capable of physical crosslinking, was investigated byin situultra-small-angle X-ray scattering (USAXS) measurement during a uniaxial stretching process. Static USAXS revealed that the molded SPNP formed a highly oriented twinned face-centered cubic (f.c.c.) lattice structure with the [11-1] plane aligned nearly parallel to the film surface in the initial state. Structural analysis ofin situUSAXS using a model of uniaxial deformation induced by rearrangement of the nanoparticles revealed that the f.c.c. lattice was distorted in the stretching direction inmore » proportion to the macroscopic strain until the strain reached 35%, and subsequently changed into other f.c.c. lattices with different orientations. The lattice distortion and structural transition behavior corresponded well to the elastic and plastic deformation regimes, respectively, observed in the stress–strain curve. The attractive interaction of the hydrogen bond is considered to form only at the top surface of the shell and then plays an effective role in cross-linking between nanoparticles. The rearrangement mechanism of the nanoparticles is well accounted for by a strong repulsive interaction between the densely grafted polymer shells of neighboring particles.« less
Atta, Ayman M; El-Mahdy, Gamal A; Al-Lohedan, Hamad A; Ezzat, Abdelrahman O
2014-07-17
Monodisperse silver nanoparticles were synthesized by a new developed method via reaction of AgNO3 and oleic acid with the addition of a trace amount of Fe3+ ions. Emulsion polymerization at room temperature was employed to prepare a core-shell silver nanoparticle with controllable particle size. N,N'-methylenebisacrylamide (MBA) and potassium peroxydisulfate (KPS) were used as a crosslinker, and as redox initiator system, respectively for crosslinking polymerization. The structure and morphology of the silver nanogels were characterized by Fourier transform infrared spectroscopy (FTIR), transmission and scanning electron microscopy (TEM and SEM). The effectiveness of the synthesized compounds as corrosion inhibitors for steel in 1 M HCl was investigated by various electrochemical techniques such as potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). Monolayers of silver nanoparticle were self-assembled on the fresh active surface of the steel electrode and have been tested as a corrosion inhibitor for steel in 1 M HCl solution. The results of polarization measurements showed that nanogel particles act as a mixed type inhibitor.
Bakalova, Rumiana; Zhelev, Zhivko; Kokuryo, Daisuke; Spasov, Lubomir; Aoki, Ichio; Saga, Tsuneo
2011-01-01
Background: One of the most attractive properties of quantum dots is their potential to extend the opportunities for fluorescent and multimodal imaging in vivo. The aim of the present study was to clarify whether the composition and structure of organic coating of nanoparticles are crucial for their application in vivo. Methods: We compared quantum dots coated with non-crosslinked amino-functionalized polyamidoamine (PAMAM) dendrimers, quantum dots encapsulated in crosslinked carboxyl-functionalized PAMAM dendrimers, and silica-shelled amino-functionalized quantum dots. A multimodal fluorescent and paramagnetic quantum dot probe was also developed and analyzed. The probes were applied intravenously in anesthetized animals for visualization of brain vasculature using two-photon excited fluorescent microscopy and visualization of tumors using fluorescent IVIS® imaging (Caliper Life Sciences, Hopkinton, MA) and magnetic resonance imaging. Results: Quantum dots coated with non-crosslinked dendrimers were cytotoxic. They induced side effects in vivo, including vasodilatation with a decrease in mean arterial blood pressure and heart rate. The quantum dots penetrated the vessels, which caused the quality of fluorescent imaging to deteriorate. Quantum dots encapsulated in crosslinked dendrimers had low cytotoxicity and were biocompatible. In concentrations <0.3 nmol quantum dots/kg bodyweight, these nanoparticles did not affect blood pressure and heart rate, and did not induce vasodilatation or vasoconstriction. PEGylation (PEG [polyethylene glycol]) was an indispensable step in development of a quantum dot probe for in vivo imaging, based on silica-shelled quantum dots. The non-PEGylated silica-shelled quantum dots possessed low colloidal stability in high-salt physiological fluids, accompanied by rapid aggregation in vivo. The conjugation of silica-shelled quantum dots with PEG1100 increased their stability and half-life in the circulation without significant enhancement of their size. In concentrations <2.5 nmol/kg bodyweight, these quantum dots did not affect the main physiological variables. It was possible to visualize capillaries, which makes this quantum dot probe appropriate for investigation of mediators of vasoconstriction, vasodilatation, and brain circulation in intact animals in vivo. The multimodal silica-shelled quantum dots allowed visualization of tumor tissue in an early stage of its development, using magnetic resonance imaging. Conclusion: The present study shows that the type and structure of organic/bioorganic shells of quantum dots determine their biocompatibility and are crucial for their application in imaging in vivo, due to the effects of the shell on the following properties: colloidal stability, solubility in physiological fluids, influence of the basic physiological parameters, and cytotoxicity. PMID:21980235
De San Luis, Alicia; Paulis, Maria; Leiza, Jose Ramon
2017-11-15
Hybrid core/shell polymer particles with co-encapsulated quantum dots (QDs) (CdSe/ZnS) and CeO 2 nanoparticles have been synthesized in a two stage semi-batch emulsion polymerization process. In the first stage, both inorganic nanoparticles are incorporated into cross-linked polystyrene (PS) particles by miniemulsion polymerization. This hybrid dispersion is then used as the seed to produce the core/shell particles by starved feeding of methyl methacrylate and divinylbenzene (MMA/DVB) monomers. The core/shell hybrid dispersions maintained in the dark exhibit stable fluorescence emission over time, and notably their fluorescence intensity increases under sunlight, likely due to the effect of the co-encapsulated CeO 2 nanoparticles that change the optical properties of the environment of the quantum dot particles. The fluorescence increase depends on the QD : CeO 2 ratio, with the 1 : 2 ratio resulting in the highest increase (280%). Furthermore, a film forming hybrid latex has been synthesized using the former core/shell PS/QD/CeO 2 /PMMA particles as seeds and feeding under semi-batch conditions methyl methacrylate, butyl acrylate and acrylic acid. Films cast from this core/shell/shell hybrid dispersion also exhibit fluorescence, and as for the core/shell latex the fluorescence increases under sunlight exposure. Interestingly, the increase in the film is at least two times higher than that in the latex, which is attributed to the additional effect of the neighboring coalesced particles containing CeO 2 affecting the environment of the QDs.
Watt, John Daniel; Bleier, Grant C.; Romero, Zachary William; ...
2018-05-15
In this paper, significant reductions recently seen in the size of wide-bandgap power electronics have not been accompanied by a relative decrease in the size of the corresponding magnetic components. To achieve this, a new generation of materials with high magnetic saturation and permeability are needed. Here, we develop gram-scale syntheses of superparamagnetic Fe/Fe xO y core–shell nanoparticles and incorporate them as the magnetic component in a strongly magnetic nanocomposite. Nanocomposites are typically formed by the organization of nanoparticles within a polymeric matrix. However, this approach can lead to high organic fractions and phase separation; reducing the performance of themore » resulting material. Here, we form aminated nanoparticles that are then cross-linked using epoxy chemistry. The result is a magnetic nanoparticle component that is covalently linked and well separated. By using this ‘matrix-free’ approach, we can substantially increase the magnetic nanoparticle fraction, while still maintaining good separation, leading to a superparamagnetic nanocomposite with strong magnetic properties.« less
DOE Office of Scientific and Technical Information (OSTI.GOV)
Watt, John Daniel; Bleier, Grant C.; Romero, Zachary William
In this paper, significant reductions recently seen in the size of wide-bandgap power electronics have not been accompanied by a relative decrease in the size of the corresponding magnetic components. To achieve this, a new generation of materials with high magnetic saturation and permeability are needed. Here, we develop gram-scale syntheses of superparamagnetic Fe/Fe xO y core–shell nanoparticles and incorporate them as the magnetic component in a strongly magnetic nanocomposite. Nanocomposites are typically formed by the organization of nanoparticles within a polymeric matrix. However, this approach can lead to high organic fractions and phase separation; reducing the performance of themore » resulting material. Here, we form aminated nanoparticles that are then cross-linked using epoxy chemistry. The result is a magnetic nanoparticle component that is covalently linked and well separated. By using this ‘matrix-free’ approach, we can substantially increase the magnetic nanoparticle fraction, while still maintaining good separation, leading to a superparamagnetic nanocomposite with strong magnetic properties.« less
Defined polymer shells on nanoparticles via a continuous aerosol-based process
NASA Astrophysics Data System (ADS)
Sigmund, Stephanie; Akgün, Ertan; Meyer, Jörg; Hubbuch, Jürgen; Wörner, Michael; Kasper, Gerhard
2014-08-01
A continuous aerosol-based process is described for the encapsulation of nanoparticles with a thin polymer shell. The process is essentially based on directed binary collisions between gas-borne core particles and liquid monomer droplets carrying opposite electrical charges, followed by photo-initiated polymerization. Once the two streams are mixed together, the process runs to completion on a time scale of about 2 min or less, required for coagulation and polymerization. Gold, silica, and sodium chloride nanoparticles were successfully coated by this technique with PHDDA [poly(hexanediol diacrylate)] and/or crosslinked PMMA [poly(methyl methacrylate)]. It was found that all core materials as well as agglomerates were wettable at room temperature and that the spreading kinetics of the monomer were fast enough to cover the core particles uniformly within the time scale provided for coagulation. The shell thickness depends on the volume ratio between core particles and monomer droplets. This was demonstrated for a combination of monodisperse silica spheres ( d = 241 nm) and polydisperse methyl methacrylate droplets, resulting in a theoretical shell thickness of 18 nm. There was very good agreement between measurements by TEM and electrical mobility spectroscopy. The results revealed that about 90 % or more of the core-shell structures were formed from 1:1 collisions between a core particle and a single monomer droplet.
NASA Astrophysics Data System (ADS)
Mao, Liucheng; Liu, Meiying; Xu, Dazhuang; Wan, Qing; Huang, Qiang; Jiang, Ruming; Shi, Yingge; Deng, Fengjie; Zhang, Xiaoyong; Wei, Yen
2017-11-01
Aggregation-induced emission (AIE) dyes based fluorescent polymeric nanoparticles (FNPs) have been intensively explored for biomedical applications. However, many of these AIE-active FNPs are relied on the self-assembly of amphiphilic copolymers, which are not stable in diluted solution. Therefore, the introduction of cross-linkages into these micelles has demonstrated to be an efficient route to overcome this stability problem and endow ultra-low critical micelle concentrations (CMC) of these AIE-active FNPs. In this work, we reported the fabrication of cross-linked AIE-active FNPs through controllable reversible addition fragmentation chain transfer polymerization by using commercially available octavinyl-T8-silsesquioxane (8-vinyl POSS) as the cross-linkage for the first time. The resultant cross-linked amphiphilic copolymers (named as PEG-POSS-PhE) are prone to self-assemble into stable core-shell nanoparticles with well water dispersity, strong red fluorescence and low CMC (0.0069 mg mL-1) in aqueous solution. More importantly, PEG-POSS-PhE FNPs possess some other properties such as high water dispersity, uniform morphology and small size, excellent biocompatibility and cellular internalization, providing great potential of PEG-POSS-PhE FNPs for biological imaging application.
Multifunctional Core–Shell Nanoparticles: Discovery of Previously Invisible Biomarkers
2011-01-01
Many low-abundance biomarkers for early detection of cancer and other diseases are invisible to mass spectrometry because they exist in body fluids in very low concentrations, are masked by high-abundance proteins such as albumin and immunoglobulins, and are very labile. To overcome these barriers, we created porous, buoyant, core–shell hydrogel nanoparticles containing novel high affinity reactive chemical baits for protein and peptide harvesting, concentration, and preservation in body fluids. Poly(N-isopropylacrylamide-co-acrylic acid) nanoparticles were functionalized with amino-containing dyes via zero-length cross-linking amidation reactions. Nanoparticles functionalized in the core with 17 different (12 chemically novel) molecular baits showed preferential high affinities (KD < 10–11 M) for specific low-abundance protein analytes. A poly(N-isopropylacrylamide-co-vinylsulfonic acid) shell was added to the core particles. This shell chemistry selectively prevented unwanted entry of all size peptides derived from albumin without hindering the penetration of non-albumin small proteins and peptides. Proteins and peptides entered the core to be captured with high affinity by baits immobilized in the core. Nanoparticles effectively protected interleukin-6 from enzymatic degradation in sweat and increased the effective detection sensitivity of human growth hormone in human urine using multiple reaction monitoring analysis. Used in whole blood as a one-step, in-solution preprocessing step, the nanoparticles greatly enriched the concentration of low-molecular weight proteins and peptides while excluding albumin and other proteins above 30 kDa; this achieved a 10,000-fold effective amplification of the analyte concentration, enabling mass spectrometry (MS) discovery of candidate biomarkers that were previously undetectable. PMID:21999289
Wang, Yongmei; Yang, Chongchong; Sun, Yan; Qiu, Fengtao; Xiang, Yang; Fu, Guoqi
2018-02-01
Surface molecular imprinting over functionalized nanoparticles has proved to be an effective approach for construction of artificial nanomaterials for protein recognition. Herein, we report a strategy for synthesis of core-shell protein-imprinted nanoparticles by the functionalization of nano-cores with ionic liquids followed by aqueous precipitation polymerization to build thermo-responsive imprinted polymer nano-shells. The immobilized ionic liquids can form multiple interactions with the protein template. The polymerization process can produce thermo-reversible physical crosslinks, which are advantageous to enhancing imprinting and facilitating template removal. With bovine hemoglobin as a model template, the imprinted nanoparticles showed temperature-sensitivity in both dispersion behaviors and rebinding capacities. Compared with the ionic-liquid-modified core nanoparticles, the imprinted particles exhibited greatly increased selectivity and two orders of magnitude higher binding affinity for the template protein. The imprinted nanoparticles achieved relatively high imprinting factor up to 5.0 and specific rebinding capacity of 67.7 mg/g, respectively. These nanoparticles also demonstrated rapid rebinding kinetics and good reproducibility after five cycles of adsorption-regeneration. Therefore, the presented approach may be viable for the fabrication of high-performance protein-imprinted nanoparticles with temperature sensitivity. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Khoee, Sepideh; Kavand, Alireza
2014-02-12
Novel pH-sensitive, biodegradable and biocompatible copolymers based on polycaprolactone-poly(ethylene glycol) (PCL/PEG) were synthesized and further modified with folic acid and/or acryloyl chloride. The mixed polymeric micelles were formed by self-assembling of folated-copolymer and non-folated-copolymer with different compositions via nanoprecipitation method. The solubilization of quercetin as anti-cancer drug by the mixed micelle with the optimized composition (folated/non-folated 20/80) was more efficient than those made of each one alone. Nanogels with different crosslinking density were produced in the presence of ethylene glycol dimethacrylate (EGDMA) as the crosslinker via a photochemical method. Interfacial crosslinking of acrylated groups were utilized to produce a core-shell spherical nanoparticle to evaluate their in-vitro drug release and degradation rate. Copyright © 2013 Elsevier Masson SAS. All rights reserved.
Radiation-induced preparation of core/shell gold/albumin nanoparticles
NASA Astrophysics Data System (ADS)
Flores, Constanza Y.; Achilli, Estefania; Grasselli, Mariano
2018-01-01
Nanoparticles (NPs) are one of the most promising nanomaterials to be used in the biomedical field. Gold NPs (Au-NPs) have been covered with monolayers of many different molecules and macromolecules to prepare different kinds of biosensors. However, these coatings based on physisorption methods are not stable enough to prepare functional nanomaterials to be used in complex mixtures or in vivo applications. The aim of this work was to prepare a protein coating of Au-NPs based on a protein multilayer covering, stabilized by a novel radiation-induced crosslinking process. Albumins from human and bovine source were added to Au-NPs suspension and followed by ethanol addition to induce protein aggregation. Samples were irradiated with a gamma source at 10 kGy to induce a protein crosslinking according to recent findings. Samples containing 30%v/v ethanol showed a plasmon peak at about 532 nm, demonstrating the presence of non-aggregated Au-NPs. Using higher ethanol concentrations, the absorbance of plasmon peak showed NP aggregation. By Dynamic Light Scattering measurements, a new particle population with an average diameter of about 60 nm was found. Moreover, TEM images showed that the NPs had spherical shape and the presence of a low-density halo around the metal core confirmed the presence of the protein shell. An irradiation dose of one kGy was enough to show changes in the plasmon peak characteristics. The increase in the chemical stability of protein shell was demonstrated by the reduction in the NP dissolution kinetics in presence of cyanate.
Omer-Mizrahi, Melany; Margel, Shlomo
2009-01-15
Core polystyrene microspheres of narrow size distribution were prepared by dispersion polymerization of styrene in a mixture of ethanol and 2-methoxy ethanol. Uniform polyglycidyl methacrylate/polystyrene core-shell micrometer-sized particles were prepared by emulsion polymerization at 73 degrees C of glycidyl methacrylate in the presence of the core polystyrene microspheres. Core-shell particles with different properties (size, surface morphology and composition) have been prepared by changing various parameters belonging to the above seeded emulsion polymerization process, e.g., volumes of the monomer glycidyl methacrylate and the crosslinker monomer ethylene glycol dimethacrylate. Magnetic Fe(3)O(4)/polyglycidyl methacrylate/polystyrene micrometer-sized particles were prepared by coating the former core-shell particles with magnetite nanoparticles via a nucleation and growth mechanism. Characterization of the various particles has been accomplished by routine methods such as light microscopy, SEM, FTIR, BET and magnetic measurements.
Hajizadeh, Solmaz; Xu, Changgang; Kirsebom, Harald; Ye, Lei; Mattiasson, Bo
2013-01-25
In this work, a new macroporous molecularly imprinted cryogel (MIP composite cryogel) was synthesized by glutaraldehyde cross-linking reaction of poly(vinyl alcohol) (PVA) particles and amino-modified molecularly imprinted core-shell nanoparticles. The MIP core-shell nanoparticles were prepared using propranolol as a template by one-pot precipitation polymerization with sequential monomer addition. The characteristics of the MIP composite cryogel were studied by scanning electron microscopy (SEM) and texture analyzer. The macroporous structure of the composite (with the pore size varying from a few micrometers to 100 μm) enabled high mass transfer of particulate-containing fluids. In a solid phase extraction (SPE) process, the efficiency and selectivity of the MIP composite cryogel were investigated, where the cryogel was used as an affinity matrix to remove propranolol from aqueous solution as well as from complex plasma sample without prior protein precipitation. The MIP composite cryogel maintained high selectivity and stability and could be used repeatedly after regeneration. Copyright © 2012 Elsevier B.V. All rights reserved.
Zuo, Huali; Gu, Zi; Cooper, Helen; Xu, Zhi Ping
2015-12-01
This article introduces a strategy for stabilizing and redispersing layered double hydroxide (LDH) nanoparticles by crosslinking bovine serum albumin (BSA) coated onto the surface. The strategy involves optimization of the amount of the crosslinking agent glutaraldehyde (GTA) to achieve minimal aggregation and ready redispersion. LDH nanoparticles were prepared by co-precipitation and hydrothermal treatment, with subsequent BSA coating at the BSA/LDH mass ratio of 5:2. BSA coated onto LDH nanoparticles was crosslinked with different amounts of GTA. Aggregation studies using dilution assays, dynamic light scattering, and zeta potential analysis indicated that severe aggregation at lower LDH nanoparticle concentrations can be prevented by proper crosslinking of BSA with GTA. The GTA-crosslinked BSA-coated nanoparticles showed excellent redispersity compared to the non-crosslinked nanoparticles. In vitro cytotoxicity and cell uptake were found to be minimally affected by GTA-crosslinking. The new strategy therefore provides a much more effective method for the prevention of LDH nanoparticle aggregation and improved LDH nanoparticle redispersion for use in a wide variety of bio-applications in vitro and in vivo. Copyright © 2015 Elsevier Inc. All rights reserved.
Industrial viable process of making nanoparticles of various shapes and interior structures
NASA Astrophysics Data System (ADS)
Wang, Xiaorong
2008-03-01
Over the past 10 years, we attempted to develop industrial viable processes which were of significance in manufacturing the nanoparticles in good quality and large volume. Our effort relied on the self-assembly concepts of block macromolecules in solutions to prepare particles with a hard core made of crosslinked plastics and a soft shell made of low Tg elastomer. Depending on the type and microstructure of the copolymers, the solvent concentration and other process parameters chosen, a variety of shell-core nano-particles of different shapes (spheres, hollow spheres, ellipsoids, cylinders, linear and branched strings, disks and etc.) and sizes (5-100 nm diameter) were reproducibly synthesized. Scale-up studies led to an optimization of the manufacturing process and the production of nanoparticles in large quantities for various product application efforts. The unique performance of those nanoparticles as performance tuning additives and novel rubber reinforcing elements was explored in rubber compounds. This review describes the synthesis methods used to produce the polymer nanoparticles, the technology to modify the particles through functionalization, the means to optimize their performance for specific applications, and the methods to use those particles in rubber compounds. Collaborators: Victor J. Foltz, Kurasch Jessica, Chenchy J. Lin, Jeff Magestrelli, Sandra Warren, Alberto Scuratti, James E. Hall, Jim Krom, Mindaugas Rackaitis, Michael W. Hayes, Pat Sadhukhan, Georg G. A. Bohm
NASA Astrophysics Data System (ADS)
Saito, Noboru; Ryuzaki, Sou; Wang, Pangpang; Park, Susie; Sakai, Nobuyuki; Tatsuma, Tetsu; Okamoto, Koichi; Tamada, Kaoru
2018-03-01
The durability of two-dimensional metal nanoparticle sheets is a crucial factor for realizing next-generation optoelectronic devices based on plasmonics such as organic light-emitting diodes. Here, we report improvements in the durability of Ag nanoparticle sheets by forming alkanedithiol (DT16) cross-linked structures between the nanoparticles. The cross-linked structures in a sheet were fabricated by the self-assembly of DT16-capped Ag nanoparticles with 10% coverage (AgDT16). The durabilities for thermal, organic solvent, and oxidation reactions of AgDT16 sheets were found to be improved owing to the cross-linked structures by comparing Ag nanoparticle sheets without the cross-linked structures. The absorbance spectra revealed that the Ag nanoparticle sheets without the structure are markedly damaged by each durability test, whereas the AgDT16 sheets remain. The molecular cross-linked structures between nanoparticles in two-dimansional metal nanoparticle sheets were found to have the potential to play a key role in the realization of plasmonic optoelectronic devices including metal nanoparticles.
Development and characterization of acrylated palm oil nanoparticles using ionizing radiation
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tajau, Rida; Yunus, Wan Md Zin Wan; Dahlan, Khairul Zaman Mohd
2012-11-27
In this study, the utilization of radiation crosslinking methods which are known as intermolecular and intramolecular crosslinking for the formation of nanoparticles of Acrylated Palm Oil (APO) in the microemulsion system that also consists of Pluronic F-127 (PF-127) surfactant was demonstrated. This microemulsion system was subjected to the ionizing radiation i.e. gamma irradiation at different doses to form the crosslinked APO nanoparticles. The effects of radiation doses on the size of APO nanoparticles were investigated using the Dynamic Light Scattering (DLS) method and their images were viewed using the Transmission Electron Microcrospy (TEM). The Fourier Transform Infra-Red (FTIR) spectroscopy wasmore » used to characterize the chemical structure and the crosslinking conversion of carbon-carbon double bond (-C = C-) of the APO nanoparticles after irradiation. As a result, the size of the APO nanoparticle decreased when the irradiation dose increased. Reduce in size might be due to the effect of intramolecular crosslinking reaction of the APO nanoparticles during irradiation process. Meanwhile, the intramolecular -C C- crosslinking conversion percentage was increased at doses below 1kGy before decreasing at the higher dose that might due to the intermolecular crosslinking of the macromolecules. This study showed that radiation crosslinking methods of polymerization and crosslinking in the microemulsion were found to be promising for the synthesis of nanoparticles.« less
Let there be light: photo-cross-linked block copolymer nanoparticles.
Roy, Debashish; Sumerlin, Brent S
2014-01-01
Polymeric nanoparticles are prepared by selectively cross-linking a photo-sensitive dimethylmaleimide-containing block of a diblock copolymer via UV irradiation. A well-defined photo-cross-linkable block copolymer is prepared via reversible addition-fragmentation chain transfer (RAFT) polymerization of a dimethylmaleimide-functional acrylamido monomer containing photoreactive pendant groups with a poly(N,N-dimethylacrylamide) (PDMA) macro-chain transfer agent. The resulting amphiphilic block copolymers form micelles in water with a hydrophilic PDMA shell and a hydrophobic photo-cross-linkable dimethylmaleimide-containing core. UV irradiation results in photodimerization of the dimethylmaleimide groups within the micelle cores to yield core-cross-linked aggregates. Alternatively, UV irradiation of homogeneous solutions of the block copolymer in a non-selective solvent leads to in situ nanoparticle formation. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Wöhl-Bruhn, S; Heim, E; Schwoerer, A; Bertz, A; Harling, S; Menzel, H; Schilling, M; Ludwig, F; Bunjes, H
2012-10-15
Hydrogels are under investigation as long term delivery systems for biomacromolecules as active pharmaceutical ingredients. The release behavior of hydrogels can be tailored during the fabrication process. This study investigates the applicability of fluxgate magnetorelaxometry (MRX) as a tool to characterize the release properties of such long term drug delivery depots. MRX is based on the use of superparamagnetic core-shell nanoparticles as model substances. The feasibility of using superparamagnetic nanoparticles to study the degradation of and the associated release from hydrogel cylinders and hydrogel microspheres was a major point of interest. Gels prepared from two types of photo crosslinkable polymers based on modified hydroxyethylstarch, specifically hydroxyethyl starch-hydroxyethyl methacrylate (HES-HEMA) and hydroxyethyl starch-polyethylene glycol methacrylate (HES-P(EG)(6)MA), were analyzed. MRX analysis of the incorporated nanoparticles allowed to evaluate the influence of different crosslinking conditions during hydrogel production as well as to follow the increase in nanoparticle mobility as a result of hydrogel degradation during release studies. Conventional release studies with fluorescent markers (half-change method) were performed for comparison. MRX with superparamagnetic nanoparticles as model substances is a promising method to analyze pharmaceutically relevant processes such as the degradation of hydrogel drug carrier systems. In contrast to conventional release experiments MRX allows measurements in closed vials (reducing loss of sample and sampling errors), in opaque media and at low magnetic nanoparticle concentrations. Magnetic markers possess a better long-term stability than fluorescent ones and are thus also promising for the use in in vivo studies. Copyright © 2012 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Ozmaian, Masoumeh; Jasnow, David; Eskandari Nasrabad, Afshin; Zilman, Anton; Coalson, Rob D.
2018-01-01
The effect of cohesive contacts or, equivalently, dynamical cross-linking on the equilibrium morphology of a polymer brush infiltrated by nanoparticles that are attracted to the polymer strands is studied for plane-grafted brushes using coarse-grained molecular dynamics and approximate statistical mechanical models. In particular, the Alexander-de Gennes (AdG) and Strong Stretching Theory (SST) mean-field theory (MFT) models are considered. It is found that for values of the MFT cross-link strength interaction parameter beyond a certain threshold, both AdG and SST models predict that the polymer brush will be in a compact state of nearly uniform density packed next to the grafting surface over a wide range of solution phase nanoparticle concentrations. Coarse grained molecular dynamics simulations confirm this prediction, for both small nanoparticles (nanoparticle volume = monomer volume) and large nanoparticles (nanoparticle volume = 27 × monomer volume). Simulation results for these cross-linked systems are compared with analogous results for systems with no cross-linking. At the same solution phase nanoparticle concentration, strong cross-linking results in additional compression of the brush relative to the non-crosslinked analog and, at all but the lowest concentrations, to a lesser degree of infiltration by nanoparticles. For large nanoparticles, the monomer density profiles show clear oscillations moving outwards from the grafting surface, corresponding to a degree of layering of the absorbed nanoparticles in the brush as they pack against the grafting surface.
Organic-dye-coupled magnetic nanoparticles encaged inside thermoresponsive PNIPAM Microcapsules.
Guo, Jia; Yang, Wuli; Deng, Yonghui; Wang, Changchun; Fu, Shoukuan
2005-07-01
We present a new approach for the fabrication of thermoresponsive polymer microcapsules with mobile magnetic cores that undergo a volume phase-transition upon changing the temperature and are collected under an external magnetic field. We have prepared organic/inorganic composite microspheres with a well-defined core-shell structure that are composed of a crosslinked poly(N-isopropylacrylamide) (PNIPAM) shell and silica cores dotted centrally by magnetite nanoparticles. Since the infiltration of template-decomposed products is dependent on the permeability of PNIPAM shells triggered by changes of exterior temperature, the silica layer sandwiched between the magnetic core and the PNIPAM shell was quantitatively removed to generate PNIPAM microcapsules with mobile magnetic cores by treatment with aqueous NaOH solution. For development of the desired multifunctional microcapsules, modification of the unetched silica surface interiors can be realized by treatment with a silane coupling agent containing functional groups that can easily bind to catalysts, enzymes, or labeling molecules. Herein, fluorescein isothiocyanate (FITC), which is a common organic dye, is attached to the insides of the mobile magnetic cores to give PNIPAM microcapsules with FITC-labeled magnetic cores. In this system, it can be expected that an extension of the functionalization of the cavity properties of smart polymer microcapsules is to immobilize other target molecules onto the mobile cores in order to introduce other desired functions in the hollow cage.
Zhong, Yinan; Zhang, Jian; Cheng, Ru; Deng, Chao; Meng, Fenghua; Xie, Fang; Zhong, Zhiyuan
2015-05-10
The existence of drug resistance poses a major obstacle for the treatment of various malignant human cancers. Here, we report on reduction-sensitive reversibly crosslinked hyaluronic acid (HA) nanoparticles based on HA-Lys-LA conjugates (Lys: l-lysine methyl ester, LA: lipoic acid) for active targeting delivery of doxorubicin (DOX) to CD44+ breast cancers in vitro and in vivo, effectively overcoming drug resistance (ADR). HA-Lys-LA with degrees of substitution of 5, 10 and 28% formed robust nano-sized nanoparticles (152-219nm) following auto-crosslinking. DOX-loaded crosslinked nanoparticles revealed inhibited DOX release under physiological conditions while fast drug release in the presence of 10mM glutathione (GSH). Notably, MTT assays showed that DOX-loaded crosslinked HA-Lys-LA10 nanoparticles possessed an apparent targetability and a superior antitumor activity toward CD44 receptor overexpressing DOX-resistant MCF-7 human breast cancer cells (MCF-7/ADR). The in vivo pharmacokinetics and biodistribution studies in MCF-7/ADR tumor xenografts in nude mice showed that DOX-loaded crosslinked HA-Lys-LA10 nanoparticles had a prolonged circulation time and a remarkably high accumulation in the tumor (12.71%ID/g). Notably, DOX-loaded crosslinked HA-Lys-LA10 nanoparticles exhibited effective inhibition of tumor growth while continuous tumor growth was observed for mice treated with free drug. The Kaplan-Meier survival curves showed that in contrast to control groups, all mice treated with DOX-loaded crosslinked HA-Lys-LA10 nanoparticles survived over an experimental period of 44days. Importantly, DOX-loaded crosslinked HA nanoparticles caused low side effects. The reversibly crosslinked hyaluronic acid nanoparticles with excellent biocompatibility, CD44-targetability, and effective reversal of drug resistance have a great potential in cancer therapy. Copyright © 2015 Elsevier B.V. All rights reserved.
Selvam, S; Rajiv Gandhi, R; Suresh, J; Gowri, S; Ravikumar, S; Sundrarajan, M
2012-09-15
Sulfated β-cyclodextrin was synthesized from sulfonation of β-cyclodextrin and sulfated polymer was crosslinked with cotton fabric using ethylenediaminetetraacetic acid as crosslinker. ZnO, TiO(2) and Ag nanoparticles were prepared and characterized by XRD, UV, DLS, SEM and PSA. The prepared nanoparticles were coated on crosslinked cotton fabric. The crosslinking and nanoparticles coating effects of cotton fabrics were studied by FTIR and SEM analysis. The antibacterial test was done against gram positive Staphylococcus aureus and gram negative Escherichia coli bacterium. Copyright © 2012 Elsevier B.V. All rights reserved.
Xiao, Kai; Lin, Tzu-Yin; Lam, Kit S; Li, Yuanpei
2017-06-14
Precision drug delivery has a great impact on the application of precision oncology for better patient care. Here we report a facile strategy for fine-tuning the stability, drug release and responsiveness of stimuli-responsive cross-linked nanoparticles towards precision drug delivery. A series of micellar nanoparticles with different levels of intramicellar disulfide crosslinkages could be conveniently produced with a mixed micelle approach. These micellar nanoparticles were all within a size range of 25-40 nm so that they could take full advantage of the enhanced permeability and retention (EPR) effect for tumor-targeted drug delivery. The properties of these nanoparticles such as critical micelle concentration (CMC), stability, drug release and responsiveness to a reductive environment could be well correlated with the levels of crosslinking (LOC). Compared to the micellar nanoparticles with a LOC at 0% that caused the death of animals of two species (mouse and rat) due to the acute toxicity such as hemolysis, the nanoparticles at all other levels of crosslinking were much safer to be administered into animals. The in vitro antitumor efficacy of micellar nanoparticles crosslinked at lower levels (20% & 50%) were much more effective than that of 100% crosslinked micellar nanoparticles in SKOV-3 ovarian cancer cells.
Elzoghby, Ahmed O; Helmy, Maged W; Samy, Wael M; Elgindy, Nazik A
2013-01-01
A novel particulate delivery matrix based on ionically crosslinked casein (CAS) nanoparticles was developed for controlled release of the poorly soluble anticancer drug flutamide (FLT). Nanoparticles were fabricated via oil-in-water emulsification then stabilized by ionic crosslinking of the positively charged CAS molecules below their isoelectric point, with the polyanionic crosslinker sodium tripolyphosphate. With the optimal preparation conditions, the drug loading and incorporation efficiency achieved were 8.73% and 64.55%, respectively. The nanoparticles exhibited a spherical shape with a size below 100 nm and a positive zeta potential (+7.54 to +17.3 mV). FLT was molecularly dispersed inside the nanoparticle protein matrix, as revealed by thermal analysis. The biodegradability of CAS nanoparticles in trypsin solution could be easily modulated by varying the sodium tripolyphosphate crosslinking density. A sustained release of FLT from CAS nanoparticles for up to 4 days was observed, depending on the crosslinking density. After intravenous administration of FLT-CAS nanoparticles into rats, CAS nanoparticles exhibited a longer circulation time and a markedly delayed blood clearance of FLT, with the half-life of FLT extended from 0.88 hours to 14.64 hours, compared with drug cosolvent. The results offer a promising method for tailoring biodegradable, drug-loaded CAS nanoparticles as controlled, long-circulating drug delivery systems of hydrophobic anticancer drugs in aqueous vehicles. PMID:23658490
Target-responsive DNAzyme cross-linked hydrogel for visual quantitative detection of lead.
Huang, Yishun; Ma, Yanli; Chen, Yahong; Wu, Xuemeng; Fang, Luting; Zhu, Zhi; Yang, Chaoyong James
2014-11-18
Because of the severe health risks associated with lead pollution, rapid, sensitive, and portable detection of low levels of Pb(2+) in biological and environmental samples is of great importance. In this work, a Pb(2+)-responsive hydrogel was prepared using a DNAzyme and its substrate as cross-linker for rapid, sensitive, portable, and quantitative detection of Pb(2+). Gold nanoparticles (AuNPs) were first encapsulated in the hydrogel as an indicator for colorimetric analysis. In the absence of lead, the DNAzyme is inactive, and the substrate cross-linker maintains the hydrogel in the gel form. In contrast, the presence of lead activates the DNAzyme to cleave the substrate, decreasing the cross-linking density of the hydrogel and resulting in dissolution of the hydrogel and release of AuNPs for visual detection. As low as 10 nM Pb(2+) can be detected by the naked eye. Furthermore, to realize quantitative visual detection, a volumetric bar-chart chip (V-chip) was used for quantitative readout of the hydrogel system by replacing AuNPs with gold-platinum core-shell nanoparticles (Au@PtNPs). The Au@PtNPs released from the hydrogel upon target activation can efficiently catalyze the decomposition of H2O2 to generate a large volume of O2. The gas pressure moves an ink bar in the V-chip for portable visual quantitative detection of lead with a detection limit less than 5 nM. The device was able to detect lead in digested blood with excellent accuracy. The method developed can be used for portable lead quantitation in many applications. Furthermore, the method can be further extended to portable visual quantitative detection of a variety of targets by replacing the lead-responsive DNAzyme with other DNAzymes.
Free-Standing and Self-Crosslinkable Hybrid Films by Core-Shell Particle Design and Processing.
Vowinkel, Steffen; Paul, Stephen; Gutmann, Torsten; Gallei, Markus
2017-11-15
The utilization and preparation of functional hybrid films for optical sensing applications and membranes is of utmost importance. In this work, we report the convenient and scalable preparation of self-crosslinking particle-based films derived by directed self-assembly of alkoxysilane-based cross-linkers as part of a core-shell particle architecture. The synthesis of well-designed monodisperse core-shell particles by emulsion polymerization is the basic prerequisite for subsequent particle processing via the melt-shear organization technique. In more detail, the core particles consist of polystyrene (PS) or poly(methyl methacrylate) (PMMA), while the comparably soft particle shell consists of poly(ethyl acrylate) (PEA) and different alkoxysilane-based poly(methacrylate)s. For hybrid film formation and convenient self-cross-linking, different alkyl groups at the siloxane moieties were investigated in detail by solid-state Magic-Angle Spinning Nuclear Magnetic Resonance (MAS, NMR) spectroscopy revealing different crosslinking capabilities, which strongly influence the properties of the core or shell particle films with respect to transparency and iridescent reflection colors. Furthermore, solid-state NMR spectroscopy and investigation of the thermal properties by differential scanning calorimetry (DSC) measurements allow for insights into the cross-linking capabilities prior to and after synthesis, as well as after the thermally and pressure-induced processing steps. Subsequently, free-standing and self-crosslinked particle-based films featuring excellent particle order are obtained by application of the melt-shear organization technique, as shown by microscopy (TEM, SEM).
Ishiwata, Takumi; Michibata, Ayano; Kokado, Kenta; Ferlay, Sylvie; Hosseini, Mir Wais; Sada, Kazuki
2018-02-06
New polymer capsules (PCs) were obtained using a crystal crosslinking (CC) method on core-shell MOF crystals. The latter are based on the epitaxial growth of two isostructural coordination polymers which are then selectively crosslinked. Decomposition of the non-reticulated phase leads to new PCs, possessing a well-defined hollow cubic shape reflecting the heterostructure of the template.
Growth model for arc-deposited fullerene-like CNx nanoparticles.
Veisz, Bernadett; Radnóczi, György
2005-06-01
Multiwall CNx nanotubes, nanoonions, and amorphous nanoballs were formed by carbon DC arc evaporation in a nitrogen atmosphere. The samples were investigated by conventional and high-resolution transmission electron microscopy. We propose a fragment-by-fragment growth mechanism for the formation of the nanoparticles. Accordingly, particles and aggregates of particles form in the vacuum ambient by the collisions between atomic species and small fragments. This growth model is supported by the discontinuous inner shells and disordered surface layers composed from graphene fragments. Image simulations confirm the detectability of dangling and back-folding surface layers in the experimental images. Further, the simulated images also confirm that the growth of nanoonions starts from a single fullerene-like seed. The amorphous nanoballs form when ordering of the building blocks during growth is hindered by the cross-linking nitrogen bonds. Copyright (c) 2005 Wiley-Liss, Inc.
Effect of curcumin caged silver nanoparticle on collagen stabilization for biomedical applications.
Srivatsan, Kunnavakkam Vinjimur; Duraipandy, N; Begum, Shajitha; Lakra, Rachita; Ramamurthy, Usha; Korrapati, Purna Sai; Kiran, Manikantan Syamala
2015-04-01
The current study aims at understanding the influence of curcumin caged silver nanoparticle (CCSNP) on stability of collagen. The results indicated that curcumin caged silver nanoparticles efficiently stabilize collagen, indicated by enhanced tensile strength, fibril formation and viscosity. The tensile strength of curcumin caged silver nanoparticle cross-linked collagen and elongation at break was also found to be higher than glutaraldehyde cross-linked collagen. The physicochemical characteristics of curcumin caged nanoparticle cross-linked collagen exhibited enhanced strength. The thermal properties were also good with both thermal degradation temperature and hydrothermal stability higher than native collagen. CD analysis showed no structural disparity in spite of superior physicochemical properties suggesting the significance of curcumin caged nanoparticle mediated cross-linking. The additional enhancement in the stabilization of collagen could be attributed to multiple sites for interaction with collagen molecule provided by curcumin caged silver nanoparticles. The results of cell proliferation and anti-microbial activity assays indicated that curcumin caged silver nanoparticles promoted cell proliferation and inhibited microbial growth making it an excellent biomaterial for wound dressing application. The study opens scope for nano-biotechnological strategies for the development of alternate non-toxic cross-linking agents facilitating multiple site interaction thereby improving therapeutic values to the collagen for biomedical application. Copyright © 2015 Elsevier B.V. All rights reserved.
A novel "modularized" optical sensor for pH monitoring in biological matrixes.
Liu, Xun; Zhang, Shang-Qing; Wei, Xing; Yang, Ting; Chen, Ming-Li; Wang, Jian-Hua
2018-06-30
A novel core-shell structure optical pH sensor is developed with upconversion nanoparticles (UCNPs) serving as the core and silica as the shell, followed by grafting bovineserumalbumin (BSA) as another shell via glutaraldehyde cross-linking. The obtained core-shell-shell structure is shortly termed as UCNPs@SiO 2 @BSA, and its surface provides a platform for loading various pH sensitive dyes, which are alike "modules" to make it feasible for measuring pHs within different pH ranges by simply regulating the type of dyes. Generally, a single pH sensitive dye is adopted to respond within a certain pH range. This study employs bromothymol blue (BTB) and rhodamine B (RhB) to facilitate their responses to pH variations within two ranges, i.e., pH 5.99-8.09 and pH 4.98-6.40, respectively, with detection by ratio-fluorescence protocol. The core-shell-shell structure offers superior sensitivity, which is tens of times more sensitive than those achieved by ratio-fluorescence approaches based on various nanostructures, and favorable stability is achieved in high ionic strength medium. In addition, this sensor exhibits superior photostability under continuous excitation at 980 nm. Thanks to the near infrared excitation in the core-shell-shell structure, it effectively avoids the self-fluorescence from biological samples and thus facilitates accurate sensing of pH in various biological sample matrixes. Copyright © 2018 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Martinez-Espinoza, Maria Isabel; Maccagno, Massimo; Thea, Sergio; Alloisio, Marina
2018-01-01
Stable hydrosols of gold and silver nanoparticles coated with the quaternary-ammonium group endowed diacetylene DAAMM (N,N,N-trimethyl-3-(pentacosa-10,12-diynamido)propan-1-ammonium) were obtained through a ligand-exchange reaction leaving the morphology of the pristine cores unmodified. Photopolymerization of the chemisorbed diacetylene shell occurred in both red and blue phases thanks to the presence of internal, H-bondable amide functions in the monomer chain, which are supposed to help the formation of a packed bilayer on the metal surfaces. Multidisciplinary characterization of the polymerized samples, including spectroscopic, morphological and thermal techniques, highlighted that differences occur in the polymerization process on gold and silver nanoparticles under different experimental conditions, suggesting a higher affinity of the trimethylammonium headgroup for gold substrates in acidic media. With respect to the extensively investigated PCDA (pentacosa-10,12-diynoic acid), DAAMM showed reduced capability of photogenerating thick polymer shells, especially in the more delocalized blue form, probably because of the inefficiency of the cationic monomer to form the multi-bilayered architecture typical of the highly-performing, carboxyl-terminated diacetylene. On the other end, the inner cross-linked structure gives to poly(DAAMM)-coated nanohybrids increased stability in water with respect to self-assembled counterparts deriving from saturated cationic surfactants, making them a promising sensing platform for rapid and cost effective assays of real samples.
Synthesis of parallel and antiparallel core-shell triangular nanoparticles
NASA Astrophysics Data System (ADS)
Bhattacharjee, Gourab; Satpati, Biswarup
2018-04-01
Core-shell triangular nanoparticles were synthesized by seed mediated growth. Using triangular gold (Au) nanoparticle as template, we have grown silver (Ag) shellto get core-shell nanoparticle. Here by changing the chemistry we have grown two types of core-shell structures where core and shell is having same symmetry and also having opposite symmetry. Both core and core-shell nanoparticles were characterized using transmission electron microscopy (TEM) and energy dispersive X-ray spectroscopy (EDX) to know the crystal structure and composition of these synthesized core-shell nanoparticles. From diffraction pattern analysis and energy filtered TEM (EFTEM) we have confirmed the crystal facet in core is responsible for such two dimensional growth of core-shell nanostructures.
Characterization of Substituted Phenol-Formaldehyde Resins Using Solid-State Carbon-13 NMR
1989-05-22
synthesized from cashew nut shell liquid, 3-n-pentadecylphenol and phenol with formaldehyde. The resulting resins were crosslinked and then investigated using...should be sent SYNOPSIS Crosslinked substituted phenol-formaldehyde resins were synthesized from cashew nut shell liquid, 3-n-pentadecylphenol and... nut shell liquid (CNSL) and are the basis for binder resins and friction particles in composite friction materials. CNSL is isolated from cashew nut
Syntheses of crosslinked latex nanoparticles using differential microemulsion polymerization
NASA Astrophysics Data System (ADS)
Hassmoro, N. F.; Rusop, M.; Abdullah, S.
2013-06-01
The differential microemulsion polymerization was used to synthesize latex nanoparticles. In this paper, 1, 3-butylene glycol dimethacrylate (1, 3-BGDMA) was used as a crosslinker respectively 1-5 weight% of monomer total. Butyl acrylate (BA), butyl methacrylate (BMA), and methacrylic acid (MAA) was used as the monomer. The thin film of latex nanoparticles were prepared by using spin coating method and have been dried at 100°C for 5 minutes. The amount of the crosslinker added in the polymerization was optimized and we found that the particle sizes fall in the range of 30-60 nm. The structural morphology of the uncrosslinked latex represented the most homogeneous image compared to the crosslinked latex. The effect of the amount of crosslinker on the particle sizes investigated by the Zeta-sizer Nano series while Atomic Force microscopy (AFM) was used to study the structural properties of latex nanoparticles.
NASA Astrophysics Data System (ADS)
Qian, Li Peng; Zhou, Li Han; Too, Heng-Phon; Chow, Gan-Moog
2011-02-01
Gold decorated NaYF4:Yb,Er/NaYF4/silica (core/shell/shell) upconversion (UC) nanoparticles ( 70-80 nm) were synthesized using tetraethyl orthosilicate and chloroauric acid in a one-step reverse microemulsion method. Gold nanoparticles ( 6 nm) were deposited on the surface of silica shell of these core/shell/shell nanoparticles. The total upconversion emission intensity (green, red, and blue) of the core/shell/shell nanoparticles decreased by 31% after Au was deposited on the surface of silica shell. The upconverted green light was coupled with the surface plasmon of Au leading to rapid heat conversion. These UC/silica/Au nanoparticles were very efficient to destroy BE(2)-C cancer cells and showed strong potential in photothermal therapy.
Zhao, Wentong; Lu, Xiaoqing; Selvaraj, Manickam; Wei, Wei; Jiang, Zhifeng; Ullah, Nabi; Liu, Jie; Xie, Jimin
2018-05-24
Low-cost electrocatalysts play an important role in the hydrogen evolution reaction (HER). Particularly, transition metal phosphides (TMPs) are widely applied in the development of HER electrocatalysts. To improve the poor electrochemical reaction kinetics of HER, we introduce a facile way to synthesize carbon core-shell materials containing cobalt phosphide nanoparticles embedded in different graphene aerogels (GAs) (CoP@C-NPs/GA-x (x = 5, 10 and 20)) using seaweed biomass as precursors. The synthesized CoP@C-NPs/GA-5 exhibits efficient catalytic activity with small overpotentials of 120 and 225 mV at current densities of 10 mA cm-2, along with the low Tafel slopes of 57 and 66 mV dec-1, for HER in acidic and alkaline electrolytes, respectively. Compared with carbon aerogel (CA) containing cobalt phosphide nanoparticles (CoP-NPs@CA), the stability of CoP@C-NPs/GA-5 coated with carbon-shells (∼0.8 nm) was significantly improved in acidic electrolytes. We also prepared carbon core-shell materials containing nickel phosphide nanoparticles embedded in GA (Ni2P@C-NPs/GA) to further expand this synthetic route. The graphene-Ni2P@C aerogel shows a similar morphology and better catalytic activity for HER in acidic and alkaline electrolytes. In this work, the robust three-dimensional (3D) GA matrix with abundant open pores and large surface area provides unblocked channels for electrolyte contact and electronic transfer and enables very close contact between the catalyst and electrolyte. The MxP@C core-shell structure prevents the inactivation of MxP NPs during HER processes, and the thin graphene oxide (GO) layers and 3D CA together build up a 3D conductive matrix, which not only adjusts the volume expansion of MxP NPs as well as preventing their aggregation, but also provides a 3D conductive pathway for rapid charge transfer processes. The present synthetic strategy for phosphides via in situ phosphorization with 3D GA can be extended to other novel high-performance catalysts. The simple synthesis and efficient catalytic activity of MXP@C-NPs/GA indicate good application prospects in HER.
Bi-metallic nanoparticles as cathode electrocatalysts
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lu, Jun; Amine, Khalil; Wang, Xiaoping
A lithium-air battery cathode catalyst includes core-shell nanoparticles on a carbon support, wherein: a core of the core-shell nanoparticles is platinum metal; and a shell of the core-shell nanoparticles is copper metal; wherein: the core-shell nanoparticles have a weight ratio of the copper metal to the platinum metal from about 4% to about 6% copper to from about 2% to about 12% platinum, with a remaining percentage being the carbon support.
Fabrication of Ni@Ti core-shell nanoparticles by modified gas aggregation source
NASA Astrophysics Data System (ADS)
Hanuš, J.; Vaidulych, M.; Kylián, O.; Choukourov, A.; Kousal, J.; Khalakhan, I.; Cieslar, M.; Solař, P.; Biederman, H.
2017-11-01
Ni@Ti core-shell nanoparticles were prepared by a vacuum based method using the gas aggregation source (GAS) of nanoparticles. Ni nanoparticles fabricated in the GAS were afterwards coated by a Ti shell. The Ti shell was deposited by means of magnetron sputtering. The Ni nanoparticles were decelerated in the vicinity of the magnetron to the Ar drift velocity in the second deposition chamber. X-ray photoelectron spectroscopy and energy dispersive x-ray spectroscopy analysis of the nanoparticles showed the core-shell structure. It was shown that the thickness of the shell can be easily tuned by the process parameters with a maximum achieved thickness of the Ti shell ~2.5 nm. The core-shell structure was confirmed by the STEM analysis of the particles.
Developing core-shell upconversion nanoparticles for optical encoding
NASA Astrophysics Data System (ADS)
Huang, Kai
Lanthanide-doped upconversion nanoparticles (UCNPs) are an emerging class of luminescent materials that emit UV or visible light under near infra-red (NIR) excitations, thereby possessing a large anti-Stokes shift property. Also considering their sharp emission bands, excellent photo- and chemical stability, and almost zero auto-fluorescence of their NIR excitation, UCNPs are advantageous for optical encoding. Fabricating core-shell structured UCNPs provides a promising strategy to tune and enhance their upconverting luminescence. However, the energy transfer between core and shell had been rarely studied. Moreover, this strategy had been limited by the difficulty of coating thick shells onto the large cores of UCNPs. To overcome these constraints, the overall aim of this project is to study the inter-layers energy transfer in core-shell UCNPs and to develop an approach for coating thicker shell onto the core UCNPs, in order to fabricate UCNPs with enhanced and tunable luminescence for optical encoding. The strategy for encapsulating UCNPs into hydrogel droplet to fabricate multi-color bead barcodes has also been developed. Firstly, to study the inter-layers energy transfer between the core and shell of coreshell UCNPs, the activator and sensitizer ions were separately doped in the core or shell by fabricating NaYF4:Er NaYF4:Yb and NaYF4:Yb NaYF4:Er UCNPs. This eliminated the intra-layer energy transfer, resulting in a luminescence that is solely based on the energy transfer between layers, which facilitated the study of inter-layers energy transfer. The results demonstrated that the NaYF4:Yb NaYF4:Er structure, with sensitizer ions doped in the core, was preferable because of the strong luminescence, through minimizing the cross relaxations between Er3+ and Yb3+ and the surface quenching. Based on these information, a strategy of enhancing and tuning upconversion luminescence of core-shell UCNPs by accumulating sensitizer in the core has been developed. Next, a strategy of coating a thick shell by lutetium doping has been developed. With a smaller ion radius compared to Y3+, when Lu3+ partially replace Y3+ in the NaYF4 UCNPs during nanoparticle synthesis, nucleation process is suppressed and the growth process is promoted, which are favorable for increasing the nanoparticle size and coating a thicker shell onto the core UCNPs. Through the rational doping of Lu3+, core UCNPs with bigger sizes and enhanced luminescence were produced. Using NaLuF4 as the shell material, shells with tremendous thickness were coated onto core UCNPs, with the shell/core ratio of up to 10:1. This led to the fabrication of multi-color UCNPs with well-designed core-shell structures with multiple layers and controllable thicknesses. Finally, a strategy of encapsulating these UCNPs to produce optically encoded micro-beads through high-throughput microfluidics has been developed. The hydrophobic UCNPs were first modified with Pluronic F127 to render them hydrophilic and uniformly distributed in the poly (ethylene glycol) diacrylate (PEGDA) hydrogel precursor. Droplets of the hydrogel precursor were formed in a microfluidic device and cross-linked into micro-beads under UV irradiation. Through encapsulation of multi-color UCNPs and by controlling their ratio, optically encoded multi-color micro-beads have been easily fabricated. These multi-color UCNPs and micro-bead barcodes have great potential for use in multiplexed bioimaging and detection.
Dmour, Isra; Taha, Mutasem O
2017-08-30
Chitosan-based nanoparticles prepared by ionotropic gelation are prone to stability issues. The aim of this work is to chemically modify chitosan by grafting to succinate, phthalate, glutarate and phenylsuccinate moieties and to investigate the suitability of the resulting polymers as covalently-crosslinked nanocarriers. Corresponding nanoparticles (NPs) were formulated by ionotropic gelation using tripolyphosphate (TPP) anion then they were covalently crosslinked using 1-ethyl-3-(3-dimethylaminopropyl)-carbodiimide (EDC). Infrared and thermal analysis confirmed the formation of phosphoramide bonds within the NPs indicating the involvement of TPP in covalent crosslinking. This is the first time to report phosphormide covalent crosslinking within nanoparticles matrices. The resulting NPs were found to resist drastic pH and calcium ion conditions. Size analysis indicated the NPs to be spherical and less than 500nm in diameter. Loading studies using Safranine O showed enhanced NPs drug loading upon covalent crosslinking compared to ionotropic gelling. Doxorubicin-loaded NPs were of superior cytotoxic properties compared to free doxorubicin. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Hamanaka, Yasushi; Yukitoki, Daichi; Kuzuya, Toshihiro
2015-09-01
AgInS2 nanoparticles were capped by ZnS via a widely used procedure to fabricate core/shell nanoparticles with highly efficient luminescence. The nanoparticle structures were investigated by ultrahigh-resolution analytical electron microscopy. We found that Zn-Ag-In-S nanoparticles were created by ZnS capping at ˜480 K, which suggests that the luminescence enhancement reported for such core/shell nanoparticles is not caused by the passivation of surface defects by ZnS shells but by Zn doping. Quasi-core/shell nanoparticles could be obtained by ZnS capping without heating. However, their luminescence efficiency remained unchanged, indicating that surface passivation was ineffective when ZnS shells were formed at room temperature.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Vlazan, P.; Ursu, D.H.; Irina-Moisescu, C.
TiO{sub 2}/ZnO core–shell nanoparticles were successfully synthesized by hydrothermal method in two stages: first stage is the hydrothermal synthesis of ZnO nanoparticles and second stage the obtained ZnO nanoparticles are encapsulated in TiO{sub 2}. The obtained ZnO, TiO{sub 2} and TiO{sub 2}/ZnO core–shell nanoparticles were investigated by means of X-ray diffraction, transmission electron microscopy, Brunauer, Emmett, Teller and resistance measurements. X-ray diffraction analysis revealed the presence of both, TiO{sub 2} and ZnO phases in TiO{sub 2}/ZnO core–shell nanoparticles. According to transmission electron microscopy images, ZnO nanoparticles have hexagonal shapes, TiO{sub 2} nanoparticles have a spherical shape, and TiO{sub 2}/ZnO core–shellmore » nanoparticles present agglomerates and the shape of particles is not well defined. The activation energy of TiO{sub 2}/ZnO core–shell nanoparticles was about 101 meV. - Graphical abstract: Display Omitted - Highlights: • TiO{sub 2}/ZnO core–shell nanoparticles were synthesized by hydrothermal method. • TiO{sub 2}/ZnO core–shell nanoparticles were investigated by means of XRD, TEM and BET. • Electrical properties of TiO{sub 2}/ZnO core–shell nanoparticles were investigated. • The activation energy of TiO{sub 2}/ZnO core–shell nanoparticles was about E{sub a} = 101 meV.« less
Characterization of Polystyrene Soft Nanoparticles Using Small Angle Neutron Scattering
NASA Astrophysics Data System (ADS)
Martin, Halie; White, Tyler; Saito, Tomonori; Dadmun, Mark
Polymer nanocomposites have become a prominent area of research recently. With a growing variety of nanoparticles available, research probing the influence of particle morphology on the overall nanocomposite properties is also increasing. Nanoparticle dispersion is controlled by both the chemical nature and morphology of the nanoparticle where a crosslinked, fuzzy organic nanoparticle is anticipated to enhance the overall miscibility and create a homogenous dispersion within a like-polymer matrix. A semi-batch microemulsion polymerization forms organic, soft nanoparticles where the precise structure of the nanoparticle is controlled by monomer rate of addition and crosslinking density. We will report small angle neutron scattering results that correlate synthetic conditions to the structural characteristics of soft nanoparticles. This analysis provides characterization of the individual nanoparticle molecular weight, the radius of the crosslinked core, the thickness of the fuzzy interfacial layer, and provides insight into the overall topography of the soft nanoparticle. This research provides a pathway to investigate the effect of nanoscale structural features of the nanoparticle on their individual properties and those of nanocomposites that contain these soft nanoparticles. DOE-BES, Division of Materials Sciences and Engineering.
Perera, Reshani H; Wu, Hanping; Peiris, Pubudu; Hernandez, Christopher; Burke, Alan; Zhang, Helen; Exner, Agata A
2017-01-01
The design of nanoscale yet highly echogenic agents for imaging outside of the vasculature and for ultrasound-mediated drug delivery remains a formidable challenge. We have previously reported on formulation of echogenic perfluoropropane gas nanobubbles stabilized by a lipid-pluronic surfactant shell. In the current work we describe the development of a new generation of these nanoparticles which consist of perfluoropropane gas stabilized by a surfactant and lipid membrane and a crosslinked network of N,N-diethylacrylamide. The resulting crosslinked nanobubbles (CL-PEG-NB) were 95.2±25.2nm in diameter and showed significant improvement in stability and retention of echogenic signal over 24h. In vivo analysis via ultrasound and fluorescence mediated tomography showed greater tumor extravasation and accumulation with CL-PEG-NB compared to microbubbles. Together these results demonstrate the capabilities and advantages of a new, more stable, nanometer-scale ultrasound contrast agent that can be utilized in future work for diagnostic scans and molecular imaging. Copyright © 2016 Elsevier Inc. All rights reserved.
Qiu, Hailong; Yang, Chunhui; Shao, Wei; Damasco, Jossana; Wang, Xianliang; Ågren, Hans; Prasad, Paras N; Chen, Guanying
2014-01-03
The luminescence efficiency of lanthanide-doped upconversion nanoparticles is of particular importance for their embodiment in biophotonic and photonic applications. Here, we show that the upconversion luminescence of typically used NaYF₄:Yb 3+ 30%/Tm 3+ 0.5% nanoparticles can be enhanced by ~240 times through a hierarchical active core/active shell/inert shell (NaYF₄:Yb 3+ 30%/Tm 3+ 0.5%)/NaYbF₄/NaYF₄ design, which involves the use of directed energy migration in the second active shell layer. The resulting active core/active shell/inert shell nanoparticles are determined to be about 11 times brighter than that of well-investigated (NaYF₄:Yb 3+ 30%/Tm 3+ 0.5%)/NaYF₄ active core/inert shell nanoparticles when excited at ~980 nm. The strategy for enhanced upconversion in Yb 3+ /Tm 3+ -codoped NaYF₄ nanoparticles through directed energy migration might have implications for other types of lanthanide-doped upconversion nanoparticles.
Influence of shell thickness on thermal stability of bimetallic Al-Pd nanoparticles
NASA Astrophysics Data System (ADS)
Wen, John Z.; Nguyen, Ngoc Ha; Rawlins, John; Petre, Catalin F.; Ringuette, Sophie
2014-07-01
Aluminum-based bimetallic core-shell nanoparticles have shown promising applications in civil and defense industries. This study addresses the thermal stability of aluminum-palladium (Al-Pd) core/shell nanoparticles with a varying shell thickness of 5, 6, and 7 Å, respectively. The classic molecular dynamics (MD) simulations are performed in order to investigate the effects of the shell thickness on the ignition mechanism and subsequent energetic processes of these nanoparticles. The histograms of temperature change and structural evolution clearly show the inhibition role of the Pd shell during ignition. While the nanoparticle with a thicker shell is more thermally stable and hence requires more excess energy, stored as the potential energy of the nanoparticle and provided through numerically heating, to initiate the thermite reaction, a higher adiabatic temperature can be produced from this nanoparticle, thanks to its greater content of Pd. The two-stage thermite reactions are discussed with their activation energy based on the energy balance processes during MD heating and production. Analyses of the simulation results reveal that the inner pressure of the core-shell nanoparticle increases with both temperature and the absorbed thermal energy during heating, which may result in a breakup of the Pd shell.
Huang, Jianbing; Li, Decai; Liang, Hui; Lu, Jiang
2017-08-01
Photo-crosslinkable and amine-containing block copolymer nanoparticles are synthesized via reversible addition-fragmentation chain transfer (RAFT) polymerization-induced self-assembly of a multifunctional core-forming monomer, 2-((3-(4-(diethylamino)phenyl)acryloyl)oxy)ethyl methacrylate (DEMA), using poly(2-hydroxypropyl methacrylate) macromolecular chain transfer agent as a steric stabilizer in methanol at 65 °C. By tuning the chain length of PDEMA, a range of nanoparticle morphologies (sphere, worm, and vesicle) can be obtained. Since cinnamate groups can easily undergo a [2 + 2] cycloaddition of the carbon-carbon double bonds upon UV irradiation, the as-prepared block copolymer nanoparticles are readily stabilized by photo-crosslinking to produce anisotropic nanoparticles. The crosslinked block copolymer nanoparticles can be used as templates for in situ formation polymer/gold hybrid nanoparticles. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Acid–base bifunctional shell cross-linked micelle nanoreactor for one-pot tandem reaction
Lee, Li -Chen; Lu, Jie; Weck, Marcus; ...
2015-12-29
In shell cross-linked micelles (SCMs) containing acid sites in the shell and base sites in the core are prepared from amphiphilic poly(2-oxazoline) triblock copolymers. These materials are utilized as two-chamber nanoreactors for a prototypical acid-base bifunctional tandem deacetalization-nitroaldol reaction. Furthermore, the acid and base sites are localized in different regions of the micelle, allowing the two steps in the reaction sequence to largely proceed in separate compartments, akin to the compartmentalization that occurs in biological systems.
Controlled release of folic acid through liquid-crystalline folate nanoparticles.
Misra, Rahul; Katyal, Henna; Mohanty, Sanat
2014-11-01
The present study explores folate nanoparticles as nano-carriers for controlled drug delivery. Cross-linked nanoparticles of liquid crystalline folates are composed of ordered stacks. This paper shows that the folate nanoparticles can be made with less than 5% loss in folate ions. In addition, this study shows that folate nanoparticles can disintegrate in a controlled fashion resulting in controlled release of the folate ions. Release can be controlled by the size of nanoparticles, the extent of cross-linking and the choice of cross-linking cation. The effect of different factors like agitation, pH, and temperature on folate release was also studied. Studies were also carried out to show the effect of release medium and role of ions in the release medium on disruption of folate assembly. Copyright © 2014. Published by Elsevier B.V.
NASA Astrophysics Data System (ADS)
Wulandari, Ika O.; Mardila, Vita T.; Santjojo, D. J. Djoko H.; Sabarudin, Akhmad
2018-01-01
The unique properties of nanomaterial provide great opportunities to develop in several fields. Several types of nanoparticles have been proven beneficial for biomedical and therapeutic agent development. Particularly for clinical use, nanoparticles must be biocompatible and non-toxic. Iron oxide nanoparticles consist of either magnetite (Fe3O4) or maghemite (γ-Fe2O3) was eligible to use for in vivo application including targeting drug delivery. Due to their distinct properties, these nanoparticles could be directed to the specific target under external magnetic field. However, nanoparticles have a tendency to form agglomeration. Therefore, surface modification was required to reduce the agglomeration. In this study, nanoparticles of Fe3O4 were produced and coated by biomaterial (chitosan) using ex-situ co-precipitation method. Nanoparticles of Fe3O4 were synthesized by adding ammonia water into iron ferric and ferrous solution. Synthesis process of Fe3O4 was conducted prior to adding chitosan. Chitosan was then cross-linked by a combination of tripolyphosphate/sulphate. The different composition ratio and crosslinking time provide the different physical and magnetic characteristics of nanoparticles. Particle and crystallite size was determined by using Scanning Electron Microscopy (SEM) and X-Ray Diffraction (XRD) respectively, whereas magnetic characteristic was determined by Electron Spin Resonance (ESR). The results showed that the ratio enhancement between chitosan: Fe3O4 increase the particle size, while decreased the crystallite size. Morphology and particle size were influenced by the ratio of crosslinkers. It was found that the higher tripolyphosphate content was contributed to the small size and more spherical morphology. In addition, the influence of crosslinking time toward crystallite size was determined by altering stirring time. The longer duration of crosslinking time, provide the larger crystallite size of chitosan-Fe3O4. There was an interesting correlation between particle size and amount of Fe3O4 phase with ESR curve.
Pi, Mengwei; Yang, Tingting; Yuan, Jianjun; Fujii, Syuji; Kakigi, Yuichi; Nakamura, Yoshinobu; Cheng, Shiyuan
2010-07-01
The nanoparticles composed of polystyrene core and poly[2-(diethylamino)ethyl methacrylate] (PDEA) hairy shell were used as colloidal templates for in situ silica mineralization, allowing the well-controlled synthesis of hybrid silica core-shell nanoparticles with raspberry-like morphology and hollow silica nanoparticles by subsequent calcination. Silica deposition was performed by simply stirring a mixture of the polymeric core-shell particles in isopropanol, tetramethyl orthosilicate (TMOS) and water at 25 degrees C for 2.5h. No experimental evidence was found for nontemplated silica formation, which indicated that silica deposition occurred exclusively in the PDEA shell and formed PDEA-silica hybrid shell. The resulting hybrid silica core-shell particles were characterized by transmission electron microscopy (TEM), thermogravimetry, aqueous electrophoresis, and X-ray photoelectron spectroscopy. TEM studies indicated that the hybrid particles have well-defined core-shell structure with raspberry morphology after silica deposition. We found that the surface nanostructure of hybrid nanoparticles and the composition distribution of PDEA-silica hybrid shell could be well controlled by adjusting the silicification conditions. These new hybrid core-shell nanoparticles and hollow silica nanoparticles would have potential applications for high-performance coatings, encapsulation and delivery of active organic molecules. 2010 Elsevier B.V. All rights reserved.
Choi, Won San; Koo, Hye Young; Kim, Dong-Yu
2008-05-06
Core-in-shell particles with controllable core size have been fabricated from core-shell particles by means of the controlled core-dissolution method. These cores in inorganic shells were employed as scaffolds for the synthesis of metal nanoparticles. After dissolution of the cores, metal nanoparticles embedded in cores were encapsulated into the interior of shell, without any damage or change. This article describes a very simple method for deriving core-in-shell particles with controllable core size and encapsulation of nanoparticles into the interior of shell.
NASA Astrophysics Data System (ADS)
Wang, Yazhou; Zhang, Yiqiong; Wang, Bochu; Cao, Yang; Yu, Qingsong; Yin, Tieying
2013-06-01
The study aimed at constructing a novel drug delivery system for programmable multiple drug release controlled with core-shell structure. The core-shell structure consisted of chitosan nanoparticles as core and polyvinylpyrrolidone micro/nanocoating as shell to form core-shell micro/nanoparticles, which was fabricated by ionic gelation and emulsion electrospray methods. As model drug agents, Naproxen and rhodamine B were encapsulated in the core and shell regions, respectively. The core-shell micro/nanoparticles thus fabricated were characterized and confirmed by scanning electron microscope, transmission electron microscope, and fluorescence optical microscope. The core-shell micro/nanoparticles showed good release controllability through drug release experiment in vitro. It was noted that a programmable release pattern for dual drug agents was also achieved by adjusting their loading regions in the core-shell structures. The results indicate that emulsion electrospraying technology is a promising approach in fabrication of core-shell micro/nanoparticles for programmable dual drug release. Such a novel multi-drug delivery system has a potential application for the clinical treatment of cancer, tuberculosis, and tissue engineering.
Lu, Annie Xi; Liu, Yijing; Oh, Hyuntaek; Gargava, Ankit; Kendall, Eric; Nie, Zhihong; DeVoe, Don L; Raghavan, Srinivasa R
2016-06-22
We describe the creation of polymeric microcapsules that can exhibit autonomous motion along defined trajectories. The capsules are made by cross-linking aqueous microdroplets of the biopolymer chitosan using glutaraldehyde. A coflow microfluidic tubing device is used to generate chitosan droplets containing nanoparticles (NPs) with an iron (Fe) core and a platinum (Pt) shell. The droplets are then incubated in a Petri dish with the cross-linking solution, and an external magnet is placed below the Petri dish to pull the NPs together as a collective "patch" on one end of each droplet. This results in cross-linked capsules (∼150 μm in diameter) with an anisotropic (patchy) structure. When these capsules are placed in a solution of H2O2, the Pt shell of the NPs catalyzes the decomposition of H2O2 into O2 gas, which is ejected from the patchy end in the form of bubbles. As a result, the capsules (which are termed micromotors) move in a direction opposite to the bubbles. Furthermore, the micromotors can be steered along specific paths by an external magnet (the magnetic response arises due to the Fe in the core of the NPs). A given micromotor can thus be directed to meet with and adhere to an inert capsule, i.e., a model cargo. Adhesion occurs due to the soft nature of the two structures. Once the cargo is picked up, the micromotor-cargo pair can be moved along a specific path to a destination, whereupon the cargo can be released from the micromotor. We believe these soft micromotors offer significant benefits over their existing hard counterparts because of their biocompatibility, biodegradability, and ability to encapsulate a variety of payloads.
Fabrication of silver nanoparticle sponge leather with durable antibacterial property.
Liu, Gongyan; Haiqi, Gao; Li, Kaijun; Xiang, Jun; Lan, Tianxiang; Zhang, Zongcai
2018-03-15
Leather product with durable antibacterial property is of great interest both from industry and consumer's point of view. To fabricate such functional leather, gallic acid modified silver nanoparticles (GA@AgNPs) were first in situ synthesized with a core-shell structure and an average size of 15.3nm. Due to its hydrophilic gallic acid surface, the GA@AgNPs possessed excellent stability and dispersibility in wide pH range from 3 to 12 and also showed effective antibacterial activity with a minimum inhibitory concentration (MIC) of around 10μgmL -1 . Then, such GA@AgNPs were used as retanning agent to be successfully filled into leather matrix during the leather manufacturing process. Moreover, taking the advantage of its high surface density of carboxyl groups, these GA@AgNPs could be further chemically cross-linked onto collagen fibers by chrome tanning agent. After retanning, the resultant leather was given a "AgNPs sponge" feature with high payload of silver nanoparticles against laundry, exhibiting high and durable antibacterial activity. Copyright © 2017 Elsevier Inc. All rights reserved.
Controlling Hydrogel Mechanics via Bio-Inspired Polymer-Nanoparticle Bond Dynamics.
Li, Qiaochu; Barrett, Devin G; Messersmith, Phillip B; Holten-Andersen, Niels
2016-01-26
Interactions between polymer molecules and inorganic nanoparticles can play a dominant role in nanocomposite material mechanics, yet control of such interfacial interaction dynamics remains a significant challenge particularly in water. This study presents insights on how to engineer hydrogel material mechanics via nanoparticle interface-controlled cross-link dynamics. Inspired by the adhesive chemistry in mussel threads, we have incorporated iron oxide nanoparticles (Fe3O4 NPs) into a catechol-modified polymer network to obtain hydrogels cross-linked via reversible metal-coordination bonds at Fe3O4 NP surfaces. Unique material mechanics result from the supra-molecular cross-link structure dynamics in the gels; in contrast to the previously reported fluid-like dynamics of transient catechol-Fe(3+) cross-links, the catechol-Fe3O4 NP structures provide solid-like yet reversible hydrogel mechanics. The structurally controlled hierarchical mechanics presented here suggest how to develop hydrogels with remote-controlled self-healing dynamics.
NASA Astrophysics Data System (ADS)
Devi, Jutika; Saikia, Rashmi; Datta, Pranayee
2016-10-01
The present paper describes the study of core-shell nanoparticles for application as nanoantenna in the optical domain. To obtain the absorption and extinction efficiencies as well as the angular distribution of the far field radiation pattern and the resonance wavelengths for these metal-dielectric, dielectric-metal and metal-metal core-shell nanoparticles in optical domain, we have used Finite Element Method based COMSOL Multiphysics Software and Mie Theory. From the comparative study of the extinction efficiencies of core-shell nanoparticles of different materials, it is found that for silica - gold core - shell nanoparticles, the resonant wavelength is greater than that of the gold - silver, silver-gold and gold-silica core - shell nanoparticles and also the radiation pattern of the silica-gold core-shell nanoparticle is the most suitable one from the point of view of directivity. The dielectric functions of the core and shell material as well as of the embedded matrix are extremely important and plays a very major role to tune the directivity and resonance wavelength. Such highly controllable parameters of the dielectric - metal core - shell nanoparticles make them suitable for efficient coupling of optical radiation into nanoscale structures for a broad range of applications in the field of communications.
Qiu, Hailong; Yang, Chunhui; Shao, Wei; Damasco, Jossana; Wang, Xianliang; Ågren, Hans; Prasad, Paras N.; Chen, Guanying
2014-01-01
The luminescence efficiency of lanthanide-doped upconversion nanoparticles is of particular importance for their embodiment in biophotonic and photonic applications. Here, we show that the upconversion luminescence of typically used NaYF4:Yb3+30%/Tm3+0.5% nanoparticles can be enhanced by ~240 times through a hierarchical active core/active shell/inert shell (NaYF4:Yb3+30%/Tm3+0.5%)/NaYbF4/NaYF4 design, which involves the use of directed energy migration in the second active shell layer. The resulting active core/active shell/inert shell nanoparticles are determined to be about 11 times brighter than that of well-investigated (NaYF4:Yb3+30%/Tm3+0.5%)/NaYF4 active core/inert shell nanoparticles when excited at ~980 nm. The strategy for enhanced upconversion in Yb3+/Tm3+-codoped NaYF4 nanoparticles through directed energy migration might have implications for other types of lanthanide-doped upconversion nanoparticles. PMID:28348285
Magnetite and magnetite/silver core/shell nanoparticles with diluted magnet-like behavior
DOE Office of Scientific and Technical Information (OSTI.GOV)
Garza-Navarro, Marco; Torres-Castro, Alejandro, E-mail: alejandro.torrescs@uanl.edu.m; Centro de Innovacion, Investigacion y Desarrollo en Ingenieria y Tecnologia, Universidad Autonoma de Nuevo Leon, Apodaca, Nuevo Leon 66600
2010-01-15
In the present work is reported the use of the biopolymer chitosan as template for the preparation of magnetite and magnetite/silver core/shell nanoparticles systems, following a two step procedure of magnetite nanoparticles in situ precipitation and subsequent silver ions reduction. The crystalline and morphological characteristics of both magnetite and magnetite/silver core/shell nanoparticles systems were analyzed by high resolution transmission electron microscopy (HRTEM) and nanobeam diffraction patterns (NBD). The results of these studies corroborate the core/shell morphology and the crystalline structure of the magnetite core and the silver shell. Moreover, magnetization temperature dependent, M(T), measurements show an unusual diluted magnetic behaviormore » attributed to the dilution of the magnetic ordering in the magnetite and magnetite/silver core/shell nanoparticles systems. - Graphical abstract: Biopolymer chitosan was used as stabilization media to synthesize both magnetite and magnetite/silver core/shell nanoparticles. Results of HRTEM and NBD patterns confirm core/shell morphology of the obtained nanoparticles. It was found that the composites show diluted magnet-like behavior.« less
Jensen, Andreas I; Binderup, Tina; Kumar EK, Pramod; Kjær, Andreas; Rasmussen, Palle H; Andresen, Thomas L
2014-05-12
Copolymers of ABC-type (PEG-PHEMA-PCMA) architecture were prepared by atom transfer radical polymerization and formulated as micelles with functionalizable primary alcohols in the shell-region (PHEMA-block) to which the metal-ion chelators DOTA or CB-TE2A were conjugated. Using this micelle system we compared the in vivo stabilities of DOTA and CB-TE2A as chelators of (64)Cu in micelle nanoparticles. The coumarin polymer (PCMA-block) micelle core was cross-linked by UV irradiation at 2 W/cm(2) for 30 min. The cross-linked micelles were labeled with (64)Cu at room temperature for 2 h (DOTA) or 80 °C for 3 h (CB-TE2A), giving labeling efficiencies of 60-76% (DOTA) and 40-47% (CB-TE2A). (64)Cu-micelles were injected into tumor-bearing mice (8 mg/kg) and PET/CT scans were carried out at 1, 22, and 46 h postinjection. The micelles showed good blood stability (T1/2: 20-26 h) and tumor uptake that was comparable with other nanoparticle systems. The DOTA micelles showed a biodistribution similar to the CB-TE2A micelles and the tumor uptake was comparable for both micelle types at 1 h (1.9% ID/g) and 22 h (3.9% ID/g) but diverged at 46 h with 3.6% ID/g (DOTA) and 4.9% ID/g (CB-TE2A). On the basis of our data, we conclude that cross-linked PEG-PHEMA-PCMA micelles have long circulating properties resulting in tumor accumulation and that DOTA and CB-TE2A (64)Cu-chelates show similar in vivo stability for the studied micelle system.
Gold core@silver semishell Janus nanoparticles prepared by interfacial etching
NASA Astrophysics Data System (ADS)
Chen, Limei; Deming, Christopher P.; Peng, Yi; Hu, Peiguang; Stofan, Jake; Chen, Shaowei
2016-07-01
Gold core@silver semishell Janus nanoparticles were prepared by chemical etching of Au@Ag core-shell nanoparticles at the air/water interface. Au@Ag core-shell nanoparticles were synthesized by chemical deposition of a silver shell onto gold seed colloids followed by the self-assembly of 1-dodecanethiol onto the nanoparticle surface. The nanoparticles then formed a monolayer on the water surface of a Langmuir-Blodgett trough, and part of the silver shell was selectively etched away by the mixture of hydrogen peroxide and ammonia in the water subphase, where the etching was limited to the side of the nanoparticles that was in direct contact with water. The resulting Janus nanoparticles exhibited an asymmetrical distribution of silver on the surface of the gold cores, as manifested in transmission electron microscopy, UV-vis absorption, and X-ray photoelectron spectroscopy measurements. Interestingly, the Au@Ag semishell Janus nanoparticles exhibited enhanced electrocatalytic activity in oxygen reduction reactions, as compared to their Au@Ag and Ag@Au core-shell counterparts, likely due to a synergistic effect between the gold cores and silver semishells that optimized oxygen binding to the nanoparticle surface.Gold core@silver semishell Janus nanoparticles were prepared by chemical etching of Au@Ag core-shell nanoparticles at the air/water interface. Au@Ag core-shell nanoparticles were synthesized by chemical deposition of a silver shell onto gold seed colloids followed by the self-assembly of 1-dodecanethiol onto the nanoparticle surface. The nanoparticles then formed a monolayer on the water surface of a Langmuir-Blodgett trough, and part of the silver shell was selectively etched away by the mixture of hydrogen peroxide and ammonia in the water subphase, where the etching was limited to the side of the nanoparticles that was in direct contact with water. The resulting Janus nanoparticles exhibited an asymmetrical distribution of silver on the surface of the gold cores, as manifested in transmission electron microscopy, UV-vis absorption, and X-ray photoelectron spectroscopy measurements. Interestingly, the Au@Ag semishell Janus nanoparticles exhibited enhanced electrocatalytic activity in oxygen reduction reactions, as compared to their Au@Ag and Ag@Au core-shell counterparts, likely due to a synergistic effect between the gold cores and silver semishells that optimized oxygen binding to the nanoparticle surface. Electronic supplementary information (ESI) available: Additional TEM, UV-vis, XPS, and electrochemical data. See DOI: 10.1039/c6nr03368g
Göktürk, Ilgım; Üzek, Recep; Uzun, Lokman; Denizli, Adil
2016-06-01
In this study, a new molecular imprinting (MIP)-based monolithic cryogel column was prepared using chemically crosslinked molecularly imprinted nanoparticles, to achieve a simplified chromatographic separation (SPE) for a model compound, L-glutamic acid (L-Glu). Cryogelation through crosslinking of imprinted nanoparticles forms stable monolithic cryogel columns. This technique reduces the leakage of nanoparticles and increases the surface area, while protecting the structural features of the cryogel for stable and efficient recognition of the template molecule. A non-imprinted monolithic cryogel column (NIP) was also prepared, using non-imprinted nanoparticles produced without the addition of L-Glu during polymerization. The molecularly imprinted monolithic cryogel column (MIP) indicates apparent recognition selectivity and a good adsorption capacity compared to the NIP. Also, we have achieved a significant increase in the adsorption capacity, using the advantage of high surface area of the nanoparticles.
NASA Astrophysics Data System (ADS)
Duan, Xiaopin; Xiao, Jisheng; Yin, Qi; Zhang, Zhiwen; Yu, Haijun; Mao, Shirui; Li, Yaping
2014-03-01
Metastasis, the main cause of cancer related deaths, remains the greatest challenge in cancer treatment. Disulfiram (DSF), which has multi-targeted anti-tumor activity, was encapsulated into redox-sensitive shell crosslinked micelles to achieve intracellular targeted delivery and finally inhibit tumor growth and metastasis. The crosslinked micelles demonstrated good stability in circulation and specifically released DSF under a reductive environment that mimicked the intracellular conditions of tumor cells. As a result, the DSF-loaded redox-sensitive shell crosslinked micelles (DCMs) dramatically inhibited cell proliferation, induced cell apoptosis and suppressed cell invasion, as well as impairing tube formation of HMEC-1 cells. In addition, the DCMs could accumulate in tumor tissue and stay there for a long time, thereby causing significant inhibition of 4T1 tumor growth and marked prevention in lung metastasis of 4T1 tumors. These results suggested that DCMs could be a promising delivery system in inhibiting the growth and metastasis of breast cancer.
Aerosol fabrication methods for monodisperse nanoparticles
Jiang, Xingmao; Brinker, C Jeffrey
2014-10-21
Exemplary embodiments provide materials and methods for forming monodisperse particles. In one embodiment, the monodisperse particles can be formed by first spraying a nanoparticle-containing dispersion into aerosol droplets and then heating the aerosol droplets in the presence of a shell precursor to form core-shell particles. By removing either the shell layer or the nanoparticle core of the core-shell particles, monodisperse nanoparticles can be formed.
Evaluating Dimethyldiethoxysilane for use in Polyurethane Crosslinked Silica Aerogels
NASA Technical Reports Server (NTRS)
Randall, Jason P.; Meador, Mary Ann B.; Jana, Sadhan C.
2008-01-01
Silica aerogels are highly porous materials which exhibit exceptionally low density and thermal conductivity. Their "pearl necklace" nanostructure, however, is inherently weak; most silica aerogels are brittle and fragile. The strength of aerogels can be improved by employing an additional crosslinking step using isocyanates. In this work, dimethyldiethoxysilane (DMDES) is evaluated for use in the silane backbone of polyurethane crosslinked aerogels. Approximately half of the resulting aerogels exhibited a core/shell morphology of hard crosslinked aerogel surrounding a softer, uncrosslinked center. Solid state NMR and scanning electron microscopy results indicate the DMDES incorporated itself as a conformal coating around the outside of the secondary silica particles, in much the same manner as isocyanate crosslinking. Response surface curves were generated from compression data, indicating levels of reinforcement comparable to that in previous literature, despite the core/shell morphology.
Synthesis and cytotoxicity study of magnesium ferrite-gold core-shell nanoparticles.
Nonkumwong, Jeeranan; Pakawanit, Phakkhananan; Wipatanawin, Angkana; Jantaratana, Pongsakorn; Ananta, Supon; Srisombat, Laongnuan
2016-04-01
In this work, the core-magnesium ferrite (MgFe2O4) nanoparticles were prepared by hydrothermal technique. Completed gold (Au) shell coating on the surfaces of MgFe2O4 nanoparticles was obtained by varying core/shell ratios via a reduction method. Phase identification, morphological evolution, optical properties, magnetic properties and cytotoxicity to mammalian cells of these MgFe2O4 core coated with Au nanoparticles were examined by using a combination of X-ray diffraction, scanning electron microscopy, transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy, UV-visible spectroscopy (UV-vis), vibrating sample magnetometry and resazurin microplate assay techniques. In general, TEM images revealed different sizes of the core-shell nanoparticles generated from various core/shell ratios and confirmed the completed Au shell coating on MgFe2O4 core nanoparticles via suitable core/shell ratio with particle size less than 100 nm. The core-shell nanoparticle size and the quality of coating influence the optical properties of the products. The UV-vis spectra of complete coated MgFe2O4-Au core-shell nanoparticles exhibit the absorption bands in the near-Infrared (NIR) region indicating high potential for therapeutic applications. Based on the magnetic property measurement, it was found that the obtained MgFe2O4-Au core-shell nanoparticles still exhibit superparamagnetism with lower saturation magnetization value, compared with MgFe2O4 core. Both of MgFe2O4 and MgFe2O4-Au core-shell also showed in vitro non-cytotoxicity to mouse areola fibroblast (L-929) cell line. Copyright © 2015 Elsevier B.V. All rights reserved.
Crosslinked polymer nanoparticles containing single conjugated polymer chains
NASA Astrophysics Data System (ADS)
Ponzio, Rodrigo A.; Marcato, Yésica L.; Gómez, María L.; Waiman, Carolina V.; Chesta, Carlos A.; Palacios, Rodrigo E.
2017-06-01
Conjugated polymer nanoparticles are widely used in fluorescent labeling and sensing, as they have mean radii between 5 and 100 nm, narrow size dispersion, high brightness, and are photochemically stable, allowing single particle detection with high spatial and temporal resolution. Highly crosslinked polymers formed by linking individual chains through covalent bonds yield high-strength rigid materials capable of withstanding dissolution by organic solvents. Hence, the combination of crosslinked polymers and conjugated polymers in a nanoparticulated material presents the possibility of interesting applications that require the combined properties of constituent polymers and nanosized dimension. In the present work, F8BT@pEGDMA nanoparticles composed of poly(ethylene glycol dimethacrylate) (pEGDMA; a crosslinked polymer) and containing the commercial conjugated polymer poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) were synthesized and characterized. Microemulsion polymerization was applied to produce F8BT@pEDGMA particles with nanosized dimensions in a ∼25% yield. Photophysical and size distribution properties of F8BT@pEDGMA nanoparticles were evaluated by various methods, in particular single particle fluorescence microscopy techniques. The results demonstrate that the crosslinking/polymerization process imparts structural rigidity to the F8BT@pEDGMA particles by providing resistance against dissolution/disintegration in organic solvents. The synthesized fluorescent crosslinked nanoparticles contain (for the most part) single F8BT chains and can be detected at the single particle level, using fluorescence microscopy, which bodes well for their potential application as molecularly imprinted polymer fluorescent nanosensors with high spatial and temporal resolution.
Water-soluble core/shell nanoparticles for proton therapy through particle-induced radiation
NASA Astrophysics Data System (ADS)
Park, Jeong Chan; Jung, Myung-Hwan; Kim, Maeng Jun; Kim, Kye-Ryung
2015-02-01
Metallic nanoparticles have been used in biomedical applications such as magnetic resonance imaging (MRI), therapy, and drug delivery systems. Metallic nanoparticles as therapeutic tools have been demonstrated using radio-frequency magnetic fields or near-infrared light. Recently, therapeutic applications of metallic nanomaterials combined with proton beams have been reported. Particle-induced radiation from metallic nanoparticles, which can enhance the therapeutic effects of proton therapy, was released when the nanoparticles were bombarded by a high-energy proton beam. Core/shell nanoparticles, especially Au-coated magnetic nanoparticles, have drawn attention in biological applications due to their attractive characteristics. However, studies on the phase transfer of organic-ligand-based core/shell nanoparticles into water are limited. Herein, we demonstrated that hydrophobic core/shell structured nanomaterials could be successfully dispersed in water through chloroform/surfactant mixtures. The effects of the core/shell nanomaterials and the proton irradiation on Escherichia coli (E. coli) were also explored.
Reconfigurable Polymer Shells on Shape-Anisotropic Gold Nanoparticle Cores.
Kim, Juyeong; Song, Xiaohui; Kim, Ahyoung; Luo, Binbin; Smith, John W; Ou, Zihao; Wu, Zixuan; Chen, Qian
2018-05-03
Reconfigurable hybrid nanoparticles made by decorating flexible polymer shells on rigid inorganic nanoparticle cores can provide a unique means to build stimuli-responsive functional materials. The polymer shell reconfiguration has been expected to depend on the local core shape details, but limited systematic investigations have been undertaken. Here, two literature methods are adapted to coat either thiol-terminated polystyrene (PS) or polystyrene-poly(acrylic acid) (PS-b-PAA) shells onto a series of anisotropic gold nanoparticles of shapes not studied previously, including octahedron, concave cube, and bipyramid. These core shapes are complex, rendering shell contours with nanoscale details (e.g., local surface curvature, shell thickness) that are imaged and analyzed quantitatively using the authors' customized analysis codes. It is found that the hybrid nanoparticles based on the chosen core shapes, when coated with the above two polymer shells, exhibit distinct shell segregations upon a variation in solvent polarity or temperature. It is demonstrated for the PS-b-PAA-coated hybrid nanoparticles, the shell segregation is maintained even after a further decoration of the shell periphery with gold seeds; these seeds can potentially facilitate subsequent deposition of other nanostructures to enrich structural and functional diversity. These synthesis, imaging, and analysis methods for the hybrid nanoparticles of anisotropically shaped cores can potentially aid in their predictive design for materials reconfigurable from the bottom up. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Optical studies of CdSe/HgSe and CdSe/Ag2Se core/shell nanoparticles embedded in gelatin
NASA Astrophysics Data System (ADS)
Azhniuk, Yu M.; Dzhagan, V. M.; Raevskaya, A. E.; Stroyuk, A. L.; Kuchmiy, S. Ya; Valakh, M. Ya; Zahn, D. R. T.
2008-11-01
CdSe/HgSe and CdSe/Ag2Se core-shell nanoparticles are obtained by colloidal synthesis from aqueous solutions in the presence of gelatin. Optical absorption, luminescence, and Raman spectra of the nanoparticles obtained are measured. The variation of the optical spectra of CdSe/HgSe and CdSe/Ag2Se core-shell nanoparticles with the shell thickness is discussed. Sharp non-monotonous variation of the photoluminescence spectra at low shell coverage is observed.
Dextran based Polymeric Micelles as Carriers for Delivery of Hydrophobic Drugs.
Mocanu, Georgeta; Nichifor, Marieta; Sacarescu, Liviu
2017-01-01
The improvement of drugs bioavailability, especially of the hydrophobic ones, by using various nanoparticles is a very exciting field of the modern research. The applicability of nano-sized shell crosslinked micelles based on dextran as supports for controlled release of several hydrophobic drugs (nystatin, rifampicin, resveratrol, and curcumin) was investigated by in vitro drug loading/release experiments. The synthesized crosslinked micelles were loaded with drugs of various hydrophobicities and their retention/release behavior was followed by dialysis procedure. Crosslinked micelles obtained from dextran with octadecyl end groups, with or without N-(2- hydroxypropyl)-N,N-dimethyl-N-benzylammonium chloride groups attached to the main dextran chains, could retain the drugs in amounts which increased with increasing drug hydrophobicity (water insolubility), as follows: 30-60 mg rifampicin/g, 70-100 mg nystatin/g, 120-144 mg resveratrol/g and 146-260 mg curcumin/g. The rate of drug release from the loaded micelles was also dependent on the drug hydrophobicity and was always slower than the free drug recovery. Antioxidant activity of curcumin and resveratrol released from the loaded micelles was preserved. The results highlighted the potential of the new nano-sized micelles as carriers for prolonged and controlled delivery of various hydrophobic drugs. Copyright© Bentham Science Publishers; For any queries, please email at epub@benthamscience.org.
Nanoparticle Delivery Of RNAi Therapeutics For Ocular Vesicant Injury
2014-12-01
micellar nanoparticles stabilized with disulfide crosslinking, hypothesizing that PEG corona on micellar nanoparticles could reduce toxicity while...micelles. This is analogous to micelle assembly, where the shape control is governed by the volume ratio of the hydrophilic ( corona ) to...self-assembly of the complexes between siRNA and LPEI-g-PEG copolymer carriers. The PEG corona and reversibly crosslinked core of the micelles enable
Efthimiadou, Eleni K; Tapeinos, Christos; Chatzipavlidis, Alexandros; Boukos, Nikos; Fragogeorgi, Eirini; Palamaris, Lazaros; Loudos, George; Kordas, George
2014-01-30
This paper deals with the synthesis, characterization and property evaluation of drug-loaded magnetic microspheres with pH-responsive cross-linked polymer shell. The synthetic procedure consists of 3 steps, of which the first two comprise the synthesis of a poly methyl methacrylate (PMMA) template and the synthesis of a shell by using acrylic acid (AA) and methyl methacrylate (MMA) as monomers, and divinyl benzene (DVB) as cross-linker. The third step of the procedure refers to the formation of magnetic nanoparticles on the microsphere's surface. AA that attaches pH-sensitivity in the microspheres and magnetic nanoparticles in the inner and the outer surface of the microspheres, enhance the efficacy of this intelligent drug delivery system (DDS), which constitutes a promising approach toward cancer therapy. A number of experimental techniques were used to characterize the resulting microspheres. In order to investigate the in vitro controlled release behavior of the synthesized microspheres, we studied the Dox release percentage under different pH conditions and under external magnetic field. Hyperthermia caused by an alternating magnetic field (AFM) is used in order to study the doxorubicin (Dox) release behavior from microspheres with pH functionality. The in vivo fate of these hybrid-microspheres was tracked by labeling them with the γ-emitting radioisotope (99m)Tc after being intravenously injected in normal mice. According to our results, microsphere present a pH depending and a magnetic heating, release behavior. As expected, labeled microspheres were mainly found in the mononuclear phagocyte system (MPS). The highlights of the current research are: (i) to illustrate the advantages of controlled release by combining hyperthermia and pH-sensitivity and (ii) to provide noninvasive, in vivo information on the spatiotemporal biodistribution of these microsphere by dynamic γ-imaging. Copyright © 2013 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Kwon, Hyun-Woo; Lim, Young-Min; Tripathy, Suraj Kumar; Kim, Byoung-Gyu; Lee, Min-Sang; Yu, Yeon-Tae
2007-04-01
On the synthesis of Au/TiO2 core-shell structure nanoparticles, the effect of the concentration of Ti4+ on the morphology and optical property of Au/TiO2 core-shell nanoparticles was examined. A gold colloid was prepared by mixing HAuCl4\\cdot4H2O and C6H5Na3\\cdot2H2O. Titanium stock solution was prepared by mixing solutions of titanium(IV) isopropoxide (TTIP) and triethanolamine (TEOA). The concentration of the Ti4+ stock solution was adjusted to 0.01-0.3 mM, and then the gold colloid was added to the Ti4+ stock solution. Au/TiO2 core-shell structure nanoparticles could be prepared by the hydrolysis of the Ti4+ stock solution at 80 °C. The size of the as-prepared Au nanoparticles was 15 nm. The thickness of the TiO2 shell on the surface of gold particles was about 10 nm. The absorption peak of the Au/TiO2 core-shell nanoparticles shifted towards the red end of the spectrum by about 3 nm because of the formation of the TiO2 shell on the surface of the gold particles. The crystal structure of the TiO2 shell showed an anatase phase. The increase in the Au crystallite size of the Au/TiO2 nanoparticles with increasing heat treatment temperature is smaller than that in the pure Au nanoparticles. This may be due to the encapsulation of Au particles with the TiO2 shell that prevents the growth of the nanoparticle nucleation.
Wang, Shengliu; Yue, Kai; Liu, Lianying; Yang, Wantai
2013-01-01
When dispersion polymerization of styrene (St) had run for 3h, after particle rapidly growing stage, 4,4'-dimethacryloyloxybenzophenone (DMABP) cross-linker was added to reaction system and photoreactive, core(PSt)-shell(Poly(St-co-DMABP)) particles with rich benzophenone (BP) groups on surface were prepared. Polymerization of DMABP could occurred mainly on the preformed core of PSt because its diffusion could be impeded by (1) compactness of particles formed at the moment of cross-linker addition (more than 80% of monomer had been consumed, particles were no longer fully swollen by monomer), (2) reduced polarity of continuous phase, and (3) immediate occurrence of cross-linking. Subsequently, photoreactive, cross-linked hollow particles were yielded by removal of uncross-linked core in THF. SEM and TEM observation demonstrated the formation of core-shell structure and improvement of shell thickness when DMABP content increased. UV-vis spectra analysis on polymer dissolved in THF indicated that there is no polymer of DMABP in core. FTIR spectra analysis and XPS measurement further revealed that BP component on particle surface was enriched when amount of DMABP increased. Finally, an anti-fouling polymer (poly (ethylene glycol), PEG) and protein of mouse IgG was immobilized on particle surface under UV irradiation, as confirmed by FTIR spectra analysis, SEM observation and TMB color reaction. Crown Copyright © 2012. Published by Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Rajbongshi, Himanshu; Bhattacharjee, Suparna; Datta, Pranayee
2017-02-01
Plasmonic Ag/ZnO core-shell nanoparticles have been synthesized via a simple two-step wet chemical method for application in Photocatalysis. The morphology, size, crystal structure, composition and optical properties of the nanoparticles are investigated by x-ray diffraction, transmission electron microscopy (TEM), FTIR spectroscopy, ultraviolet-visible (UV-Vis) absorption spectroscopy and photoluminescence (PL) spectroscopy. The shell thicknesses are varied by varying the concentration of zinc nitrate hexa-hydrate and triethanolamine. The ZnO shell coating over Ag core enhances the charge separation, whereas the larger shell thickness and increased refractive index of surrounding medium cause red shifts of surface Plasmon resonance (SPR) peak of Ag core. The photoluminescence (PL) spectra of Ag/ZnO core-shell show that the larger shell thickness quenches the near band edge UV emission of ZnO. The electrochemical impedance spectra (EIS) i.e. Nyquist plots also confirm the higher charge transfer efficiency of the Ag/ZnO core-shell nanoparticles. The Photocatalytic activities of Ag/ZnO core-shell nanoparticles are investigated by the degradation of methylene blue (MB) dye under direct sunlight irradiation. Compared to pure ZnO nanoparticles (NPs), Ag/ZnO core-shell NPs display efficient sunlight plasmonic photocatalytic activity because of the influence of SPR of Ag core and the electron sink effect. The photocatalytic activity of Ag/ZnO core-shell NPs is found to be enhanced with increase in shell thickness.
Strain distribution of confined Ge/GeO2 core/shell nanoparticles engineered by growth environments
NASA Astrophysics Data System (ADS)
Wei, Wenyan; Yuan, Cailei; Luo, Xingfang; Yu, Ting; Wang, Gongping
2016-02-01
The strain distributions of Ge/GeO2 core/shell nanoparticles confined in different host matrix grown by surface oxidation are investigated. The simulated results by finite element method demonstrated that the strains of the Ge core and the GeO2 shell strongly depend on the growth environments of the nanoparticles. Moreover, it can be found that there is a transformation of the strain on Ge core from tensile to compressive strain during the growth of Ge/GeO2 core/shell nanoparticles. And, the transformation of the strain is closely related with the Young's modulus of surrounding materials of Ge/GeO2 core/shell nanoparticles.
One-pot synthesis of monodisperse CoFe2O4@Ag core-shell nanoparticles and their characterization.
Hara, Shuta; Aisu, Jumpei; Kato, Masahiro; Aono, Takashige; Sugawa, Kosuke; Takase, Kouichi; Otsuki, Joe; Shimizu, Shigeru; Ikake, Hiroki
2018-06-08
In recent years, monodispersed magnetic nanoparticles with a core/shell structure are expected for their wide applications including magnetic fluid, recoverable catalysts, and biological analysis. However, their synthesis method needs numerous processes such as solvent substitution, exchange of protective agents, and centrifugation. A simple and rapid method for the synthesis of monodispersed core-shell nanoparticles makes it possible to accelerate their further applications. This paper describes a simple and rapid one-pot synthesis of core (CoFe 2 O 4 )-shell (Ag) nanoparticles with high monodispersity. The synthesized nanoparticles showed plasmonic light absorption owing to the Ag shell. Moreover, the magnetic property of the nanoparticles had a soft magnetic behavior at room temperature and a hard magnetic behavior at 5 K. In addition, the nanoparticles showed high monodispersity with a low polydispersity index (PDI) value of 0.083 in hexane.
Electrosprayed core-shell polymer-lipid nanoparticles for active component delivery
NASA Astrophysics Data System (ADS)
Eltayeb, Megdi; Stride, Eleanor; Edirisinghe, Mohan
2013-11-01
A key challenge in the production of multicomponent nanoparticles for healthcare applications is obtaining reproducible monodisperse nanoparticles with the minimum number of preparation steps. This paper focus on the use of electrohydrodynamic (EHD) techniques to produce core-shell polymer-lipid structures with a narrow size distribution in a single step process. These nanoparticles are composed of a hydrophilic core for active component encapsulation and a lipid shell. It was found that core-shell nanoparticles with a tunable size range between 30 and 90 nm and a narrow size distribution could be reproducibly manufactured. The results indicate that the lipid component (stearic acid) stabilizes the nanoparticles against collapse and aggregation and improves entrapment of active components, in this case vanillin, ethylmaltol and maltol. The overall structure of the nanoparticles produced was examined by multiple methods, including transmission electron microscopy and differential scanning calorimetry, to confirm that they were of core-shell form.
One-pot synthesis of monodisperse CoFe2O4@Ag core-shell nanoparticles and their characterization
NASA Astrophysics Data System (ADS)
Hara, Shuta; Aisu, Jumpei; Kato, Masahiro; Aono, Takashige; Sugawa, Kosuke; Takase, Kouichi; Otsuki, Joe; Shimizu, Shigeru; Ikake, Hiroki
2018-06-01
In recent years, monodispersed magnetic nanoparticles with a core/shell structure are expected for their wide applications including magnetic fluid, recoverable catalysts, and biological analysis. However, their synthesis method needs numerous processes such as solvent substitution, exchange of protective agents, and centrifugation. A simple and rapid method for the synthesis of monodispersed core-shell nanoparticles makes it possible to accelerate their further applications. This paper describes a simple and rapid one-pot synthesis of core (CoFe2O4)-shell (Ag) nanoparticles with high monodispersity. The synthesized nanoparticles showed plasmonic light absorption owing to the Ag shell. Moreover, the magnetic property of the nanoparticles had a soft magnetic behavior at room temperature and a hard magnetic behavior at 5 K. In addition, the nanoparticles showed high monodispersity with a low polydispersity index (PDI) value of 0.083 in hexane.
NASA Astrophysics Data System (ADS)
Zhang, Lingyan; Han, Fei
2018-04-01
Bovine serum albumin (BSA) modified gold nanoparticles (AuNPs) was selected as template for the synthesis of AuNPs@gold nanoclusters (AuNCs) core/shell nanoparticles, in which BSA not only acted as dual functions agent for both anchoring and reducing Au3+ ions, but also was employed as a bridge between the AuNPs and AuNCs. Optical properties of AuNPs@AuNCs core/shell nanoparticles were studied using UV-visible and fluorescence spectroscopy. The prepared AuNPs@AuNCs core/shell nanoparticles exhibited sphere size uniformity with improved monodispersity, excellent fluorescence and fluorescent stability. Compared with AuNCs, AuNPs@AuNCs core/shell nanoparticles possessed large size and strong fluorescence intensity due to the effect of AuNPs as core. Moreover, the mechanism of the AuNPs induced fluorescence changes of the core/shell nanoparticles was first explored.
Gold core@silver semishell Janus nanoparticles prepared by interfacial etching.
Chen, Limei; Deming, Christopher P; Peng, Yi; Hu, Peiguang; Stofan, Jake; Chen, Shaowei
2016-08-14
Gold core@silver semishell Janus nanoparticles were prepared by chemical etching of Au@Ag core-shell nanoparticles at the air/water interface. Au@Ag core-shell nanoparticles were synthesized by chemical deposition of a silver shell onto gold seed colloids followed by the self-assembly of 1-dodecanethiol onto the nanoparticle surface. The nanoparticles then formed a monolayer on the water surface of a Langmuir-Blodgett trough, and part of the silver shell was selectively etched away by the mixture of hydrogen peroxide and ammonia in the water subphase, where the etching was limited to the side of the nanoparticles that was in direct contact with water. The resulting Janus nanoparticles exhibited an asymmetrical distribution of silver on the surface of the gold cores, as manifested in transmission electron microscopy, UV-vis absorption, and X-ray photoelectron spectroscopy measurements. Interestingly, the Au@Ag semishell Janus nanoparticles exhibited enhanced electrocatalytic activity in oxygen reduction reactions, as compared to their Au@Ag and Ag@Au core-shell counterparts, likely due to a synergistic effect between the gold cores and silver semishells that optimized oxygen binding to the nanoparticle surface.
Self-reporting and refoldable profluorescent single-chain nanoparticles.
Fischer, Tobias S; Spann, Sebastian; An, Qi; Luy, Burkhard; Tsotsalas, Manuel; Blinco, James P; Mutlu, Hatice; Barner-Kowollik, Christopher
2018-05-28
We pioneer the formation of self-reporting and refoldable profluorescent single-chain nanoparticles (SCNPs) via the light-induced reaction ( λ max = 320 nm) of nitroxide radicals with a photo-active crosslinker. Whereas the tethered nitroxide moiety in these polymers fully quenches the luminescence ( i.e. fluorescence) of the aromatic backbone, nitroxide trapping of a transient C-radical leads to the corresponding closed shell alkoxyamine thereby restoring luminescence of the folded SCNP. Hence, the polymer in the folded state is capable of emitting light, while in the non-folded state the luminescence is silenced. Under oxidative conditions the initially folded SCNPs unfold, resulting in luminescence switch-off and the reestablishment of the initial precursor polymer. Critically, we show that the luminescence can be repeatedly silenced and reactivated. Importantly, the self-reporting character of the SCNPs was followed by size-exclusion chromatography (SEC), dynamic light scattering (DLS), fluorescence, electron paramagnetic resonance (EPR), nuclear magnetic resonance (NMR) and diffusion ordered NMR spectroscopy (DOSY).
Zhang, Junjie; Li, Benqiang; Yue, Huijuan; Wang, Jing; Zheng, Yuansuo
2018-01-01
With the combined surface imprinting technique and immobilized template strategy, molecularly imprinted magnetic nanoparticles were successfully prepared and coupled with high-performance liquid chromatography to selectively separate and determine gallic acid from the pomegranate rind. On the surface of carboxyl-functionalized magnetic nanospheres, thin imprinting shells were formed using dopamine as monomer and crosslinker. The characteristics, polymerization conditions, and adsorption performances of the resultant nanomaterials were investigated in detail. In addition of good crystallinity, satisfactory magnetism, and uniform morphology of the obtained polymers, they had rapid binding kinetics, high adsorption capacity, and favorable reusability. In the mixed solution of four hydroxybenzoic acids, the prepared nanomaterials have an excellent selectivity to gallic acid with an imprinting factor of as high as 17.5. Therefore, the polymers have great potentials in specific extraction and enrichment of gallic acid from the complex natural resources. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Temperature-responsive nanogel multilayers of poly(N-vinylcaprolactam) for topical drug delivery.
Zavgorodnya, Oleksandra; Carmona-Moran, Carlos A; Kozlovskaya, Veronika; Liu, Fei; Wick, Timothy M; Kharlampieva, Eugenia
2017-11-15
We report nanothin temperature-responsive hydrogel films of poly(N-vinylcaprolactam) nanoparticles (νPVCL) with remarkably high loading capacity for topical drug delivery. Highly swollen (νPVCL) n multilayer hydrogels, where n denotes the number of nanoparticle layers, are produced by layer-by-layer hydrogen-bonded assembly of core-shell PVCL-co-acrylic acid nanoparticles with linear PVPON followed by cross-linking of the acrylic acid shell with either ethylene diamine (EDA) or adipic acid dihydrazide (AAD). We demonstrate that a (νPVCL) 5 film undergoes dramatic and reversible swelling up to 9 times its dry thickness at pH = 7.5, indicating 89v/v % of water inside the network. These hydrogels exhibit highly reversible ∼3-fold thickness changes with temperature variations from 25 to 50°C at pH = 5, the average pH of human skin. We also show that a (νPVCL) 30 hydrogel loaded with ∼120µgcm -2 sodium diclofenac, a non-steroidal anti-inflammatory drug used for osteoarthritis pain management, provides sustained permeation of this drug through an artificial skin membrane for up to 24h at 32°C (the average human skin surface temperature). The cumulative amount of diclofenac transported at 32°C from the (νPVCL) 30 hydrogel after 24h is 12 times higher than that from the (νPVCL) 30 hydrogel at 22°C. Finally, we demonstrate that the (νPVCL) hydrogels can be used for multiple drug delivery by inclusion of Nile red, fluorescein and DAPI dyes within the νPVCL nanoparticles prior to hydrogel assembly. Using confocal microscopy we observed the presence of separate dye-loaded νPVCL compartments within the hydrogel matrix with all three dyes confined to the nanogel particles without intermixing between the dyes. Our study provides opportunity for development of temperature-responsive multilayer hydrogel coatings made via the assembly of core-shell nanogel particles which can be used for skin-sensitive materials for topical drug delivery. Copyright © 2017 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Yang, Chungja
Nanoparticles are fascinating where physical and optical properties are related to size. Highly controllable synthesis methods and nanoparticle assembly are essential for highly innovative technological applications. Well-defined shaped and sized nanoparticles enable comparisons between experiments, theory and subsequent new models to explain experimentally observed phenomena. Among nanoparticles, nonhomogeneous core-shell nanoparticles (CSnp) have new properties that arise when varying the relative dimensions of the core and the shell. This CSnp structure enables various optical resonances, and engineered energy barriers, in addition to the high charge to surface ratio. Assembly of homogeneous nanoparticles into functional structures has become ubiquitous in biosensors (i.e. optical labeling), nanocoatings, and electrical circuits. Limited nonhomogenous nanoparticle assembly has only been explored. Many conventional nanoparticle assembly methods exist, but this work explores dielectrophoresis (DEP) as a new method. DEP is particle polarization via non-uniform electric fields while suspended in conductive fluids. Most prior DEP efforts involve microscale particles. Prior work on core-shell nanoparticle assemblies and separately, nanoparticle characterizations with dielectrophoresis and electrorotation, did not systematically explore particle size, dielectric properties (permittivity and electrical conductivity), shell thickness, particle concentration, medium conductivity, and frequency. This work is the first, to the best of our knowledge, to systematically examine these dielectrophoretic properties for core-shell nanoparticles. Further, we conduct a parametric fitting to traditional core-shell models. These biocompatible core-shell nanoparticles were studied to fill a knowledge gap in the DEP field. Experimental results (chapter 5) first examine medium conductivity, size and shell material dependencies of dielectrophoretic behaviors of spherical CSnp into 2D and 3D particle-assemblies. Chitosan (amino sugar) and poly-L-lysine (amino acid, PLL) CSnp shell materials were custom synthesized around a hollow (gas) core by utilizing a phospholipid micelle around a volatile fluid templating for the shell material; this approach proves to be novel and distinct from conventional core-shell models wherein a conductive core is coated with an insulative shell. Experiments were conducted within a 100 nl chamber housing 100 um wide Ti/Au quadrapole electrodes spaced 25 um apart. Frequencies from 100kHz to 80MHz at fixed local field of 5Vpp were tested with 10-5 and 10-3 S/m medium conductivities for 25 seconds. Dielectrophoretic responses of ~220 and 340(or ~400) nm chitosan or PLL CSnp were compiled as a function of medium conductivity, size and shell material. Experiments further examined shell thickness and particle concentration (chapter 6) dependencies on ~530 nm CSnp dielectrophoretic and electrorotational responses with ~30nm and ~80 nm shell thicknesses and at particle concentration count rates of 5000 +/- 500, 10000 +/- 500, and 15000 +/- 500 counts per second. Using similar experimental conditions, both dielectrophoretic and electrorotational CSnp responses were compiled versus frequency, shell thickness, and particle concentration. Knowledge gained from this study includes a unique resonance-like dielectrophoretic and electrorotational spectrum, which is significantly distinct from other cells and particles. CSnp dielectric properties were then calculated by parametrically fitting parameters to an existing core-shell model. The optimum conductivity and relative permittivity for the core and the shell are 1E-15 S/m, 1, 0.6 S/m, and 90, respectively. These properties can be exploited to rapidly assemble these unique core-shell particles for future structural color production in fabrics, vehicle, and wall painting.
Mandal, Samir; Chaudhuri, Keya
2016-02-26
Magnetic core shell nanoparticles are composed of a highly magnetic core material surrounded by a thin shell of desired drug, polymer or metal oxide. These magnetic core shell nanoparticles have a wide range of applications in biomedical research, more specifically in tissue imaging, drug delivery and therapeutics. The present review discusses the up-to-date knowledge on the various procedures for synthesis of magnetic core shell nanoparticles along with their applications in cancer imaging, drug delivery and hyperthermia or cancer therapeutics. Literature in this area shows that magnetic core shell nanoparticle-based imaging, drug targeting and therapy through hyperthermia can potentially be a powerful tool for the advanced diagnosis and treatment of various cancers.
Boron-based nanostructures: Synthesis, functionalization, and characterization
NASA Astrophysics Data System (ADS)
Bedasso, Eyrusalam Kifyalew
Boron-based nanostructures have not been explored in detail; however, these structures have the potential to revolutionize many fields including electronics and biomedicine. The research discussed in this dissertation focuses on synthesis, functionalization, and characterization of boron-based zero-dimensional nanostructures (core/shell and nanoparticles) and one-dimensional nanostructures (nanorods). The first project investigates the synthesis and functionalization of boron-based core/shell nanoparticles. Two boron-containing core/shell nanoparticles, namely boron/iron oxide and boron/silica, were synthesized. Initially, boron nanoparticles with a diameter between 10-100 nm were prepared by decomposition of nido-decaborane (B10H14) followed by formation of a core/shell structure. The core/shell structures were prepared using the appropriate precursor, iron source and silica source, for the shell in the presence of boron nanoparticles. The formation of core/shell nanostructures was confirmed using high resolution TEM. Then, the core/shell nanoparticles underwent a surface modification. Boron/iron oxide core/shell nanoparticles were functionalized with oleic acid, citric acid, amine-terminated polyethylene glycol, folic acid, and dopamine, and boron/silica core/shell nanoparticles were modified with 3-(amino propyl) triethoxy silane, 3-(2-aminoethyleamino)propyltrimethoxysilane), citric acid, folic acid, amine-terminated polyethylene glycol, and O-(2-Carboxyethyl)polyethylene glycol. A UV-Vis and ATR-FTIR analysis established the success of surface modification. The cytotoxicity of water-soluble core/shell nanoparticles was studied in triple negative breast cancer cell line MDA-MB-231 and the result showed the compounds are not toxic. The second project highlights optimization of reaction conditions for the synthesis of boron nanorods. This synthesis, done via reduction of boron oxide with molten lithium, was studied to produce boron nanorods without any contamination and with a uniform size distribution. Various reaction parameters such as temperature, reaction time, and sonication were altered to find the optimal reaction conditions. Once these conditions were determined, boron nanorods were produced then functionalized with amine-terminated polyethylene glycol.
Hu, Kun; Huang, Xiaoxia; Gao, Yongqing; Huang, Xulin; Xiao, Hang; McClements, David Julian
2015-09-01
Biopolymer core-shell nanoparticles were fabricated using a hydrophobic protein (zein) as the core and a hydrophilic polysaccharide (pectin) as the shell. Particles were prepared by coating cationic zein nanoparticles with anionic pectin molecules using electrostatic deposition (pH 4). The core-shell nanoparticles were fortified with curcumin (a hydrophobic bioactive molecule) at a high loading efficiency (>86%). The resulting nanoparticles were spherical, relatively small (diameter ≈ 250 nm), and had a narrow size distribution (polydispersity index ≈ 0.24). The encapsulated curcumin was in an amorphous (rather than crystalline form) as detected by differential scanning calorimetry (DSC). Fourier transform infrared (FTIR) and Raman spectra indicated that the encapsulated curcumin interacted with zein mainly through hydrophobic interactions. The nanoparticles were converted into a powdered form that had good water-dispersibility. These core-shell biopolymer nanoparticles could be useful for incorporating curcumin into functional foods and beverages, as well as dietary supplements and pharmaceutical products. Copyright © 2015 Elsevier Ltd. All rights reserved.
DNA nanoparticles with core-shell morphology.
Chandran, Preethi L; Dimitriadis, Emilios K; Lisziewicz, Julianna; Speransky, Vlad; Horkay, Ferenc
2014-10-14
Mannobiose-modified polyethylenimines (PEI) are used in gene therapy to generate nanoparticles of DNA that can be targeted to the antigen-presenting cells of the immune system. We report that the sugar modification alters the DNA organization within the nanoparticles from homogenous to shell-like packing. The depth-dependent packing of DNA within the nanoparticles was probed using AFM nano-indentation. Unmodified PEI-DNA nanoparticles display linear elastic properties and depth-independent mechanics, characteristic of homogenous materials. Mannobiose-modified nanoparticles, however, showed distinct force regimes that were dependent on indentation depth, with 'buckling'-like response that is reproducible and not due to particle failure. By comparison with theoretical studies of spherical shell mechanics, the structure of mannobiosylated particles was deduced to be a thin shell with wall thickness in the order of few nanometers, and a fluid-filled core. The shell-core structure is also consistent with observations of nanoparticle denting in altered solution conditions, with measurements of nanoparticle water content from AFM images, and with images of DNA distribution in Transmission Electron Microscopy.
Volume-labeled nanoparticles and methods of preparation
Wang, Wei; Gu, Baohua; Retterer, Scott T; Doktycz, Mitchel J
2015-04-21
Compositions comprising nanosized objects (i.e., nanoparticles) in which at least one observable marker, such as a radioisotope or fluorophore, is incorporated within the nanosized object. The nanosized objects include, for example, metal or semi-metal oxide (e.g., silica), quantum dot, noble metal, magnetic metal oxide, organic polymer, metal salt, and core-shell nanoparticles, wherein the label is incorporated within the nanoparticle or selectively in a metal oxide shell of a core-shell nanoparticle. Methods of preparing the volume-labeled nanoparticles are also described.
Introduction of biotin or folic acid into polypyrrole magnetite core-shell nanoparticles
DOE Office of Scientific and Technical Information (OSTI.GOV)
Nan, Alexandrina; Turcu, Rodica; Liebscher, Jürgen
2013-11-13
In order to contribute to the trend in contemporary research to develop magnetic core shell nanoparticles with better properties (reduced toxicity, high colloidal and chemical stability, wide scope of application) in straightforward and reproducible methods new core shell magnetic nanoparticles were developed based on polypyrrole shells functionalized with biotin and folic acid. Magnetite nanoparticles stabilized by sebacic acid were used as magnetic cores. The morphology of magnetite was determined by transmission electron microscopy TEM, while the chemical structure investigated by FT-IR.
In Situ Generation of Two-Dimensional Au–Pt Core–Shell Nanoparticle Assemblies
2010-01-01
Two-dimensional assemblies of Au–Pt bimetallic nanoparticles are generated in situ on polyethyleneimmine (PEI) silane functionalized silicon and indium tin oxide (ITO) coated glass surfaces. Atomic force microscopy (AFM), UV–Visible spectroscopy, and electrochemical measurements reveal the formation of core–shell structure with Au as core and Pt as shell. The core–shell structure is further supported by comparing with the corresponding data of Au nanoparticle assemblies. Static contact angle measurements with water show an increase in hydrophilic character due to bimetallic nanoparticle generation on different surfaces. It is further observed that these Au–Pt core–shell bimetallic nanoparticle assemblies are catalytically active towards methanol electro-oxidation, which is the key reaction for direct methanol fuel cells (DMFCs). PMID:20651923
Chen, Hongwei; Dong, Weiling; Ge, Jun; Wang, Changhong; Wu, Xiaodong; Lu, Wei; Chen, Liwei
2013-01-01
We report the synthesis of ultrafine S nanoparticles with diameter 10 ~ 20 nm via a membrane-assisted precipitation technique. The S nanoparticles were then coated with conducting poly (3,4-ethylenedioxythiophene) (PEDOT) to form S/PEDOT core/shell nanoparticles. The ultrasmall size of S nanoparticles facilitates the electrical conduction and improves sulfur utilization. The encapsulation of conducting PEDOT shell restricts the polysulfides diffusion, alleviates self-discharging and the shuttle effect, and thus enhances the cycling stability. The resulting S/PEDOT core/shell nanoparticles show initial discharge capacity of 1117 mAh g(-1) and a stable capacity of 930 mAh g(-1) after 50 cycles.
Chen, Hongwei; Dong, Weiling; Ge, Jun; Wang, Changhong; Wu, Xiaodong; Lu, Wei; Chen, Liwei
2013-01-01
We report the synthesis of ultrafine S nanoparticles with diameter 10 ~ 20 nm via a membrane-assisted precipitation technique. The S nanoparticles were then coated with conducting poly (3,4-ethylenedioxythiophene) (PEDOT) to form S/PEDOT core/shell nanoparticles. The ultrasmall size of S nanoparticles facilitates the electrical conduction and improves sulfur utilization. The encapsulation of conducting PEDOT shell restricts the polysulfides diffusion, alleviates self-discharging and the shuttle effect, and thus enhances the cycling stability. The resulting S/PEDOT core/shell nanoparticles show initial discharge capacity of 1117 mAh g−1 and a stable capacity of 930 mAh g−1 after 50 cycles. PMID:23714786
NASA Astrophysics Data System (ADS)
Chen, Hongwei; Dong, Weiling; Ge, Jun; Wang, Changhong; Wu, Xiaodong; Lu, Wei; Chen, Liwei
2013-05-01
We report the synthesis of ultrafine S nanoparticles with diameter 10 ~ 20 nm via a membrane-assisted precipitation technique. The S nanoparticles were then coated with conducting poly (3,4-ethylenedioxythiophene) (PEDOT) to form S/PEDOT core/shell nanoparticles. The ultrasmall size of S nanoparticles facilitates the electrical conduction and improves sulfur utilization. The encapsulation of conducting PEDOT shell restricts the polysulfides diffusion, alleviates self-discharging and the shuttle effect, and thus enhances the cycling stability. The resulting S/PEDOT core/shell nanoparticles show initial discharge capacity of 1117 mAh g-1 and a stable capacity of 930 mAh g-1 after 50 cycles.
Wakaskar, Rajesh R; Bathena, Sai Praneeth R; Tallapaka, Shailendra B; Ambardekar, Vishakha V; Gautam, Nagsen; Thakare, Rhishikesh; Simet, Samantha M; Curran, Stephen M; Singh, Rakesh K; Dong, Yuxiang; Vetro, Joseph A
2015-03-01
Determine the feasibility and potential benefit of peripherally cross-linking the shell of core-shell polymer micelles on the premature release of physically loaded hydrophobic drug in whole blood and subsequent potency against solid tumors. Individual Pluronic F127 polymer micelles (F127 PM) peripherally cross-linked with ethylenediamine at 76% of total PEO blocks (X-F127 PM) were physically loaded with combretastatin A4 (CA4) by the solid dispersion method and compared to CA4 physically loaded in uncross-linked F127 PM, CA4 in DMSO in vitro, or water-soluble CA4 phosphate (CA4P) in vivo. X-F127 PM had similar CA4 loading and aqueous solubility as F127 PM up to 10 mg CA4 / mL at 22.9 wt% and did not aggregate in PBS or 90% (v/v) human serum at 37°C for at least 24 h. In contrast, X-F127 PM decreased the unbound fraction of CA4 in whole blood (fu) and increased the mean plasma residence time and subsequent potency of CA4 against the vascular function and growth of primary murine 4T1 breast tumors over CA4 in F127 PM and water-soluble CA4P after IV administration. Given that decreasing the fu is an indication of decreased drug release, peripherally cross-linking the shell of core-shell polymer micelles may be a simple approach to decrease premature release of physically loaded hydrophobic drug in the blood and increase subsequent potency in solid tumors.
Synthesis and properties MFe2O4 (M = Fe, Co) nanoparticles and core-shell structures
NASA Astrophysics Data System (ADS)
Yelenich, O. V.; Solopan, S. O.; Greneche, J. M.; Belous, A. G.
2015-08-01
Individual Fe3-xO4 and CoFe2O4 nanoparticles, as well as Fe3-xO4/CoFe2O4 core/shell structures were synthesized by the method of co-precipitation from diethylene glycol solutions. Core/shell structure were synthesized with CoFe2O4-shell thickness of 1.0, 2.5 and 3.5 nm. X-ray diffraction patterns of individual nanoparticles and core/shell are similar and indicate that all synthesized samples have a cubic spinel structure. Compares Mössbauer studies of CoFe2O4, Fe3-xO4 nanoparticles indicate superparamagnetic properties at 300 K. It was shown that individual magnetite nanoparticles are transformed into maghemite through oxidation during the synthesis procedure, wherein the smallest nanoparticles are completely oxidized while a magnetite core does occur in the case of the largest nanoparticles. The Mössbauer spectra of core/shell nanoparticles with increasing CoFe2O4-shell thickness show a gradual decrease in the relative intensity of the quadrupole doublet and significant decrease of the mean isomer shift value at both RT and 77 K indicating a decrease of the superparamagnetic relaxation phenomena. Specific loss power for the prepared ferrofluids was experimentally calculated and it was determined that under influence of ac-magnetic field magnetic fluid based on individual CoFe2O4 and Fe3-xO4 particles are characterized by very low heating temperature, when magnetic fluids based on core/shell nanoparticles demonstrate higher heating effect.
NASA Astrophysics Data System (ADS)
Jang, Haeyun; Lee, Chaedong; Nam, Gi-Eun; Quan, Bo; Choi, Hyuck Jae; Yoo, Jung Sun; Piao, Yuanzhe
2016-02-01
The difficulty in delineating tumor is a major obstacle for better outcomes in cancer treatment of patients. The use of single-imaging modality is often limited by inadequate sensitivity and resolution. Here, we present the synthesis and the use of monodisperse iron oxide nanoparticles coated with fluorescent silica nano-shells for fluorescence and magnetic resonance dual imaging of tumor. The as-synthesized core-shell nanoparticles were designed to improve the accuracy of diagnosis via simultaneous tumor imaging with dual imaging modalities by a single injection of contrast agent. The iron oxide nanocrystals ( 11 nm) were coated with Rhodamine B isothiocyanate-doped silica shells via reverse microemulsion method. Then, the core-shell nanoparticles ( 54 nm) were analyzed to confirm their size distribution by transmission electron microscopy and dynamic laser scattering. Photoluminescence spectroscopy was used to characterize the fluorescent property of the dye-doped silica shell-coated nanoparticles. The cellular compatibility of the as-prepared nanoparticles was confirmed by a trypan blue dye exclusion assay and the potential as a dual-imaging contrast agent was verified by in vivo fluorescence and magnetic resonance imaging. The experimental results show that the uniform-sized core-shell nanoparticles are highly water dispersible and the cellular toxicity of the nanoparticles is negligible. In vivo fluorescence imaging demonstrates the capability of the developed nanoparticles to selectively target tumors by the enhanced permeability and retention effects and ex vivo tissue analysis was corroborated this. Through in vitro phantom test, the core/shell nanoparticles showed a T2 relaxation time comparable to Feridex® with smaller size, indicating that the as-made nanoparticles are suitable for imaging tumor. This new dual-modality-nanoparticle approach has promised for enabling more accurate tumor imaging.
Li, Zhuo; Wang, Yong; Ni, Yongnian; Kokot, Serge
2015-08-15
A magnetic and fluorescent nano-composite was prepared. It comprised of a core of Fe3O4 nanoparticles (NPs), a silica shell and satellitic Au nano-clusters (AuNCs) capped with bovine serum albumin (BSA). This nano-composite has many desirable properties, e.g. magnetism, red emission, high water solubility, and high resistance to photo-bleaching. On addition of the analyte, 6-mercaptopurine (6-MP) or indeed other similar thiols, AuNCs formed aggregates because the existing cross-links within the Fe3O4 NPs@SiO2 and AuNC structure were broken in favor of the gold-thiol bonds. On suitable irradiation of such aggregates, red fluorescence was emitted at 613 nm. It decreased significantly as a function of the added 6-MP concentration, and the quenching ratio (F0 - F) / F0 was related linearly to the concentration of 6-MP in the range of 0.01 to 0.5 μmol L(-1). The detection limit was 0.004 μmol L(-1) (S/N=3). The method was strongly selective for 6-MP in the presence of oxidants, phenols, heavy-metal ions, and especially bio-thiols. Copyright © 2015 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Cheng, Hai-Xia; Wang, Xiao-Xu; Beijing Computing Center, Beijing 100094
Ag@ZnO core-shell nanoparticles of around 72 atoms have been investigated by the density functional theory, revealing proving for the first time that the core-shell structure exhibits a shrinkage phenomenon from outer shell in agreement with the other studies in literatures. Our calculations predict that the Ag@ZnO core-shell structure is a ferromagnetic spin polarized state, and the magnetism mainly stems from the spin splitting of 2p electrons of O atoms. In addition, the total and partial DOS of Ag@ZnO indicate that the nanostructure is a half-metallic nanoparticle and has the characters of the p-type semiconductor. Furthermore, the optical properties calculations showmore » that the absorption edge of Ag@ZnO have a red shift and good photocatalysis compare to that of the bulk ZnO. These results of the Ag@ZnO core-shell structure obtain a well agreement with the experimental measurement. - Graphical abstract: Geometric structure of (a) Ag@ZnO core-shell nanostructure; (b) the core of Ag; (c) the shell of ZnO The core-shell nanoparticle Ag@ZnO contains Ag inner core of radius of 4 Å and ZnO outer shell with thickness of 2 Å. Ag@ZnO core-shell nanoparticles of around 72 atoms have been proved for the first time that the core-shell structure exhibit a shrinkage phenomenon from outer shell. Our calculations predict that the Ag@ZnO core-shell structure is a half-metallic nanoparticle and has the characters of the p-type semiconductor. The absorption edge of Ag@ZnO have a red shift and get good photo-catalysis compare to that of the bulk ZnO.« less
Abdul Ghafoor Raja, Maria; Katas, Haliza; Jing Wen, Thum
2015-01-01
Chitosan (CS) nanoparticles have been extensively studied for siRNA delivery; however, their stability and efficacy are highly dependent on the types of cross-linker used. To address this issue, three common cross-linkers; tripolyphosphate (TPP), dextran sulphate (DS) and poly-D-glutamic acid (PGA) were used to prepare siRNA loaded CS-TPP/DS/PGA nanoparticles by ionic gelation method. The resulting nanoparticles were compared with regard to their physicochemical properties including particle size, zeta potential, morphology, binding and encapsulation efficiencies. Among all the formulations prepared with different cross linkers, CS-TPP-siRNA had the smallest particle size (ranged from 127 ± 9.7 to 455 ± 12.9 nm) with zeta potential ranged from +25.1 ± 1.5 to +39.4 ± 0.5 mV, and high entrapment (>95%) and binding efficiencies. Similarly, CS-TPP nanoparticles showed better siRNA protection during storage at 4˚C and as determined by serum protection assay. TEM micrographs revealed the assorted morphology of CS-TPP-siRNA nanoparticles in contrast to irregular morphology displayed by CS-DS-siRNA and CS-PGA-siRNA nanoparticles. All siRNA loaded CS-TPP/DS/PGA nanoparticles showed initial burst release followed by sustained release of siRNA. Moreover, all the formulations showed low and concentration-dependent cytotoxicity with human colorectal cancer cells (DLD-1), in vitro. The cellular uptake studies with CS-TPP-siRNA nanoparticles showed successful delivery of siRNA within cytoplasm of DLD-1 cells. The results demonstrate that ionically cross-linked CS-TPP nanoparticles are biocompatible non-viral gene delivery system and generate a solid ground for further optimization studies, for example with regard to steric stabilization and targeting. PMID:26068222
Platinum-coated non-noble metal-noble metal core-shell electrocatalysts
Adzic, Radoslav; Zhang, Junliang; Mo, Yibo; Vukmirovic, Miomir
2015-04-14
Core-shell particles encapsulated by a thin film of a catalytically active metal are described. The particles are preferably nanoparticles comprising a non-noble core with a noble metal shell which preferably do not include Pt. The non-noble metal-noble metal core-shell nanoparticles are encapsulated by a catalytically active metal which is preferably Pt. The core-shell nanoparticles are preferably formed by prolonged elevated-temperature annealing of nanoparticle alloys in an inert environment. This causes the noble metal component to surface segregate and form an atomically thin shell. The Pt overlayer is formed by a process involving the underpotential deposition of a monolayer of a non-noble metal followed by immersion in a solution comprising a Pt salt. A thin Pt layer forms via the galvanic displacement of non-noble surface atoms by more noble Pt atoms in the salt. The overall process is a robust and cost-efficient method for forming Pt-coated non-noble metal-noble metal core-shell nanoparticles.
Zhang, Lu; Feng, Qiang; Wang, Jiuling; Zhang, Shuai; Ding, Baoquan; Wei, Yujie; Dong, Mingdong; Ryu, Ji-Young; Yoon, Tae-Young; Shi, Xinghua; Sun, Jiashu; Jiang, Xingyu
2015-10-27
The functionalized lipid shell of hybrid nanoparticles plays an important role for improving their biocompatibility and in vivo stability. Yet few efforts have been made to critically examine the shell structure of nanoparticles and its effect on cell-particle interaction. Here we develop a microfluidic chip allowing for the synthesis of structurally well-defined lipid-polymer nanoparticles of the same sizes, but covered with either lipid-monolayer-shell (MPs, monolayer nanoparticles) or lipid-bilayer-shell (BPs, bilayer nanoparticles). Atomic force microscope and atomistic simulations reveal that MPs have a lower flexibility than BPs, resulting in a more efficient cellular uptake and thus anticancer effect than BPs do. This flexibility-regulated cell-particle interaction may have important implications for designing drug nanocarriers.
2009-10-01
nanoparticles size of 8 nm; found out that shell loaded image is much more effective than core loaded one. We have prepared a number of lipid nanoparticles ...strategies: lipid - conjugated fluorochrome was introduced into either core or shell lipids of the nanoparticles . Pyro- CE-OA that contains cholesterol... lipids either in the core or in the shell . We have conjugated the nanoparticles with the integrin ligands. We have showed
Profound Interfacial Effects in CoFe2O4/Fe3O4 and Fe3O4/CoFe2O4 Core/Shell Nanoparticles
NASA Astrophysics Data System (ADS)
Polishchuk, Dmytro; Nedelko, Natalia; Solopan, Sergii; Ślawska-Waniewska, Anna; Zamorskyi, Vladyslav; Tovstolytkin, Alexandr; Belous, Anatolii
2018-03-01
Two sets of core/shell magnetic nanoparticles, CoFe2O4/Fe3O4 and Fe3O4/CoFe2O4, with a fixed diameter of the core ( 4.1 and 6.3 nm for the former and latter sets, respectively) and thickness of shells up to 2.5 nm were synthesized from metal chlorides in a diethylene glycol solution. The nanoparticles were characterized by X-ray diffraction, transmission electron microscopy, and magnetic measurements. The analysis of the results of magnetic measurements shows that coating of magnetic nanoparticles with the shells results in two simultaneous effects: first, it modifies the parameters of the core-shell interface, and second, it makes the particles acquire combined features of the core and the shell. The first effect becomes especially prominent when the parameters of core and shell strongly differ from each other. The results obtained are useful for optimizing and tailoring the parameters of core/shell spinel ferrite magnetic nanoparticles for their use in various technological and biomedical applications.
Core-shell Au-Pd nanoparticles as cathode catalysts for microbial fuel cell applications
Yang, Gaixiu; Chen, Dong; Lv, Pengmei; Kong, Xiaoying; Sun, Yongming; Wang, Zhongming; Yuan, Zhenhong; Liu, Hui; Yang, Jun
2016-01-01
Bimetallic nanoparticles with core-shell structures usually display enhanced catalytic properties due to the lattice strain created between the core and shell regions. In this study, we demonstrate the application of bimetallic Au-Pd nanoparticles with an Au core and a thin Pd shell as cathode catalysts in microbial fuel cells, which represent a promising technology for wastewater treatment, while directly generating electrical energy. In specific, in comparison with the hollow structured Pt nanoparticles, a benchmark for the electrocatalysis, the bimetallic core-shell Au-Pd nanoparticles are found to have superior activity and stability for oxygen reduction reaction in a neutral condition due to the strong electronic interaction and lattice strain effect between the Au core and the Pd shell domains. The maximum power density generated in a membraneless single-chamber microbial fuel cell running on wastewater with core-shell Au-Pd as cathode catalysts is ca. 16.0 W m−3 and remains stable over 150 days, clearly illustrating the potential of core-shell nanostructures in the applications of microbial fuel cells. PMID:27734945
Spherical Nucleic Acids: A New Form of DNA
NASA Astrophysics Data System (ADS)
Cutler, Joshua Isaac
Spherical Nucleic Acids (SNAs) are a new class of nucleic acid-based nanomaterials that exhibit unique properties currently being explored in the contexts of gene-based cancer therapies and in the design of programmable nanoparticle-based materials. The properties of SNAs differ from canonical, linear nucleic acids by virtue of their dense packing into an oriented 3-dimensional array. SNAs can be synthesized from a number of useful nanoparticle templates, such as plasmonic gold and silver, magnetic oxides, luminescent semi-conductor quantum dots, and silica. In addition, by crosslinking the oligonucleotides and dissolving the core, they can be made in a hollow form as well. This dissertation describes the evolution of SNAs from initial studies of inorganic nanoparticle-based materials densely functionalized with oligonucleotides to the proving of a hypothesis that their unique properties can be observed in a core-less structure if the nucleic acids are densely packed and highly oriented. Chapter two describes the synthesis of densely functionalized polyvalent oligonucleotide superparamagnetic iron oxide nanoparticles using the copper-catalyzed azide-alkyne cycloaddition reaction. These particles are shown to exhibit cooperative binding in a density- and salt concentration-dependent fashion, with nearly identical behaviors to those of SNA-functionalized gold nanoparticles. Importantly, these particles are the first non-gold particles shown to be capable of entering cells in high numbers via the SNA-mediated cellular uptake pathway, and provided the first evidence that SNA-mediated cellular uptake is core-independent. In the third chapter, a gold nanoparticle catalyzed alkyne cross-linking reaction is described that is capable of forming hollow organic nanoparticles using polymers with alkyne-functionalized backbones. With this method, the alkyne-modified polymers adsorb to the particle surfaces, cross-link on the surface, allowing the gold nanoparticle to be subsequently dissolved oxidatively with KCN or Iodine. The reaction pathway is analyzed through characterization of the reaction progression and resulting products, and a mechanistic pathway is proposed. This is the first report of a gold nanoparticle catalyzed reaction involving the conversion of propargyl ethers to terminal alcohols, which can subsequently cross-link if densely arranged on a gold nanoparticle surface. Importantly, these structures can be synthesized using gold nanoparticles of a range of sizes, thereby providing control over the size and properties of the resulting crosslinked particle. Chapter four returns to the topic of SNAs and builds upon the chemistry of chapter three culminating in the synthesis of cross-linked hollow SNA nanoparticles. These structures are formed by the cross-linking of synthetically modified alkyne-bearing oligonucleotides through the pathway described in chapter three. When the gold core is dissolved, the resulting hollow SNAs exhibit nearly identical binding, nuclease resistance, cellular uptake, and gene regulation properties of SNA-gold nanoparticle conjugates. Indeed, this chapter demonstrates that the unique properties of SNA-nanoparticle conjugates are core-independent and stem solely from the dense ensemble of oligonucleotides arranged on their surfaces. The fifth chapter further asserts the synthetic achievements made in chapter four by showing how hollow SNAs can be substituted for SNA-gold nanoparticles in the context of DNA-programmable assembly. In this case, they can be used as building blocks within binary synthetic schemes to synthesize unique nanoparticle superlattices. It bolsters the design rules of DNA-programmable assembly by showing that the predicted structures form based on the behavior of SNA hybridization, and are universal for any SNA-functionalized nanoparticle.
NASA Astrophysics Data System (ADS)
Surnar, Bapurao; Sharma, Kavita; Jayakannan, Manickam
2015-10-01
Platinum drug delivery against the detoxification of cytoplasmic thiols is urgently required for achieving efficacy in breast cancer treatment that is over expressed by glutathione (GSH, thiol-oligopeptide). GSH-resistant polymer-cisplatin core-shell nanoparticles were custom designed based on biodegradable carboxylic functional polycaprolactone (PCL)-block-poly(ethylene glycol) diblock copolymers. The core of the nanoparticle was fixed as 100 carboxylic units and the shell part was varied using various molecular weight poly(ethylene glycol) monomethyl ethers (MW of PEGs = 100-5000 g mol-1) as initiator in the ring-opening polymerization. The complexation of cisplatin aquo species with the diblocks produced core-shell nanoparticles of 75 nm core with precise size control the particles up to 190 nm. The core-shell nanoparticles were found to be stable in saline solution and PBS and they exhibited enhanced stability with increase in the PEG shell thickness at the periphery. The hydrophobic PCL layer on the periphery of the cisplatin core behaved as a protecting layer against the cytoplasmic thiol residues (GSH and cysteine) and exhibited <5% of drug detoxification. In vitro drug-release studies revealed that the core-shell nanoparticles were ruptured upon exposure to lysosomal enzymes like esterase at the intracellular compartments. Cytotoxicity studies were performed both in normal wild-type mouse embryonic fibroblast cells (Wt-MEFs), and breast cancer (MCF-7) and cervical cancer (HeLa) cell lines. Free cisplatin and polymer drug core-shell nanoparticles showed similar cytotoxicity effects in the HeLa cells. In MCF-7 cells, the free cisplatin drug exhibited 50% cell death whereas complete cell death (100%) was accomplished by the polymer-cisplatin core-shell nanoparticles. Confocal microscopic images confirmed that the core-shell nanoparticles were taken up by the MCF-7 and HeLa cells and they were accumulated both at the cytoplasm as well at peri-nuclear environments. The present investigation lays a new foundation for the polymer-based core-shell nanoparticles approach for overcoming detoxification in platinum drugs for the treatment of GSH over-expressed breast cancer cells.Platinum drug delivery against the detoxification of cytoplasmic thiols is urgently required for achieving efficacy in breast cancer treatment that is over expressed by glutathione (GSH, thiol-oligopeptide). GSH-resistant polymer-cisplatin core-shell nanoparticles were custom designed based on biodegradable carboxylic functional polycaprolactone (PCL)-block-poly(ethylene glycol) diblock copolymers. The core of the nanoparticle was fixed as 100 carboxylic units and the shell part was varied using various molecular weight poly(ethylene glycol) monomethyl ethers (MW of PEGs = 100-5000 g mol-1) as initiator in the ring-opening polymerization. The complexation of cisplatin aquo species with the diblocks produced core-shell nanoparticles of 75 nm core with precise size control the particles up to 190 nm. The core-shell nanoparticles were found to be stable in saline solution and PBS and they exhibited enhanced stability with increase in the PEG shell thickness at the periphery. The hydrophobic PCL layer on the periphery of the cisplatin core behaved as a protecting layer against the cytoplasmic thiol residues (GSH and cysteine) and exhibited <5% of drug detoxification. In vitro drug-release studies revealed that the core-shell nanoparticles were ruptured upon exposure to lysosomal enzymes like esterase at the intracellular compartments. Cytotoxicity studies were performed both in normal wild-type mouse embryonic fibroblast cells (Wt-MEFs), and breast cancer (MCF-7) and cervical cancer (HeLa) cell lines. Free cisplatin and polymer drug core-shell nanoparticles showed similar cytotoxicity effects in the HeLa cells. In MCF-7 cells, the free cisplatin drug exhibited 50% cell death whereas complete cell death (100%) was accomplished by the polymer-cisplatin core-shell nanoparticles. Confocal microscopic images confirmed that the core-shell nanoparticles were taken up by the MCF-7 and HeLa cells and they were accumulated both at the cytoplasm as well at peri-nuclear environments. The present investigation lays a new foundation for the polymer-based core-shell nanoparticles approach for overcoming detoxification in platinum drugs for the treatment of GSH over-expressed breast cancer cells. Electronic supplementary information (ESI) available: TGA profile and DSC thermogram of all polymers, DLS data, AFM image, 1H-NMR, 13C-NMR, and MALDI spectra of all polymers and monomers. See DOI: 10.1039/c5nr04963f
NASA Astrophysics Data System (ADS)
Hubenthal, Frank; Ziegler, Torsten; Hendrich, Christian; Träger, Frank
2004-03-01
For many applications like surface enhanced Raman scattering in which the optical field enhancement associated with surface plasmon excitation is exploited, tunability of this collective resonance over a wide range is required. For this purpose we have prepared Ag/Au core shell and Ag/Au alloyed nanoparticles with different shell thicknesses and different percentages of the two metals. The nanoparticles were made by subsequent deposition of Ag and Au atoms on dielectric substrates followed by diffusion and nucleation or heat treatment. Depending on the Au shell thickness the plasmon frequency can be tuned, e.g. from 2.8 eV (442 nm) to 2.1 eV (590 nm). Annealing of the core-shell nanoparticles causes a shift of the resonance frequency to 2.6 eV. Theoretical modelling allows us to attribute this observation to the production of alloyed nanoparticles. Possible application of the Ag/Au nanoparticles will be discussed.
Lee, Kee-Won; Wang, Shanfeng; Yaszemski, Michael J.; Lu, Lichun
2008-01-01
A series of crosslinkable nanocomposites has been developed using hydroxyapatite (HA) nanoparticles and poly(propylene fumarate) (PPF). PPF/HA nanocomposites with four different weight fractions of HA nanoparticles have been characterized in terms of thermal and mechanical properties. To assess surface chemistry of crosslinked PPF/HA nanocomposites, their hydrophilicity and capability of adsorbing proteins have been determined using static contact angle measurement and MicroBCA protein assay kit after incubation with 10% fetal bovine serum (FBS), respectively. In vitro cell studies have been performed using MC3T3-E1 mouse pre-osteoblast cells to investigate the ability of PPF/HA nanocomposites to support cell attachment, spreading, and proliferation after 1, 4, and 7 days. By adding HA nanoparticles to PPF, the mechanical properties of crosslinked PPF/HA nanocomposites have not been increased due to the initially high modulus of crosslinked PPF. However, hydrophilicity and serum protein adsorption on the surface of nanocomposites have been significantly increased, resulting in enhanced cell attachment, spreading, and proliferation after 4 days of cell seeding. These results indicate that crosslinkable PPF/HA nanocomposites are useful for hard tissue replacement because of excellent mechanical strength and osteoconductivity. PMID:18403013
Mocanu, Georgeta; Nichifor, Marieta; Stanciu, Magdalena C
2015-03-30
Micelles formed in aqueous solution by dextran with hydrophobic (alkyl) end-groups were stabilized through divinyl sulfone crosslinking of the dextran shell. The efficacy of the crosslinking reaction was influenced by the divinyl sulfone amount, the pH and micelle concentration. Crosslinked micelles with a moderate crosslinking degree were further functionalized by attachment of 10 and 17 moles% N-(2-hydroxypropyl)-N,N-dimethyl-N-benzylammonium chloride groups along the dextran chain. The size and shape of both crosslinked micelles and their cationic derivatives were analyzed by DLS and TEM. The prepared micelles were able to bind anionic diclofenac (60-370 mg/g), hydrophobic anionic indometacin (70-120 mg/g), and hydrophobic alpha-tocopherol (170-220 mg/g) or ergocalciferol (90-110 mg/g) by hydrophobic or/and electrostatic forces. The release experiments and the antioxidant activity of bound alpha-tocopherol highlighted the potential of the new nano-sized micelles mainly as carriers for prolonged and controlled delivery of hydrophobic drugs. Copyright © 2014 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Nakatsuka, Matthew Allan Masao
Microbubbles, consisting of gas-filled cores encapsulated within phospholipid or polymer shells, are the most widely used ultrasound contrast agents in the world. Because of their acoustic impedance mismatch with surrounding tissues and compressible gaseous interiors, they have high echogenicities that allow for efficient backscatter of ultrasound. They can also generate unique harmonic frequencies when insonated near their resonance frequency, depending on physical microbubble properties such as the stiffness and thickness of the encapsulating shell. Microbubbles are used to detect a number of cardiovascular diseases, but current methodologies lack the ability to detect and distinguish small, rapidly growing abnormalities that do not produce visible blockage or slowing of blood flow. This work describes the development, formulation, and validation of microbubbles with various polymer shell architectures designed to modulate their acoustic ability. We demonstrate that the addition of a thick disulfide crosslinked, poly(acrylic acid) encapsulating shell increases a bubble's resistance to cavitation and changes its resonance frequency. Modification of this shell architecture to use hybridized DNA strands to form crosslinks between the polymer chains allows for tuning of the bubble acoustic response. When the DNA crosslinks are in place, shell stiffness is increased so the bubbles do not oscillate and acoustic signal is muted. Subsequently, when these DNA strands are displaced, partial acoustic activity is restored. By using aptamer sequences with a specific affinity towards the biomolecule thrombin as the DNA crosslinking strand, this acoustic "ON/OFF" behavior can be specifically tailored towards the presence of a specific biomarker, and produces a change in acoustic signal at concentrations of thrombin consistent with acute deep venous thrombosis. Incorporation of the emulsifying agent poly(ethylene glycol) into the encapsulating shell improves microbubble yield and circulation half-life substantially, allowing for the in vivo detection of a blood clot in a rabbit model. The results presented here show a unique marriage of highly specific molecular imaging and sonography that could be tailored towards a wide variety of cardiovascular abnormalities.
Structural and Magnetic Response in Bimetallic Core/Shell Magnetic Nanoparticles
Nairan, Adeela; Khan, Usman; Iqbal, Munawar; Khan, Maaz; Javed, Khalid; Riaz, Saira; Naseem, Shahzad; Han, Xiufeng
2016-01-01
Bimagnetic monodisperse CoFe2O4/Fe3O4 core/shell nanoparticles have been prepared by solution evaporation route. To demonstrate preferential coating of iron oxide onto the surface of ferrite nanoparticles X-ray diffraction (XRD), High resolution transmission electron microscope (HR-TEM) and Raman spectroscopy have been performed. XRD analysis using Rietveld refinement technique confirms single phase nanoparticles with average seed size of about 18 nm and thickness of shell is 3 nm, which corroborates with transmission electron microscopy (TEM) analysis. Low temperature magnetic hysteresis loops showed interesting behavior. We have observed large coercivity 15.8 kOe at T = 5 K, whereas maximum saturation magnetization (125 emu/g) is attained at T = 100 K for CoFe2O4/Fe3O4 core/shell nanoparticles. Saturation magnetization decreases due to structural distortions at the surface of shell below 100 K. Zero field cooled (ZFC) and Field cooled (FC) plots show that synthesized nanoparticles are ferromagnetic till room temperature and it has been noticed that core/shell sample possess high blocking temperature than Cobalt Ferrite. Results indicate that presence of iron oxide shell significantly increases magnetic parameters as compared to the simple cobalt ferrite. PMID:28335200
Biomimetic synthesis of chiral erbium-doped silver/peptide/silica core-shell nanoparticles (ESPN)
NASA Astrophysics Data System (ADS)
Mantion, Alexandre; Graf, Philipp; Florea, Ileana; Haase, Andrea; Thünemann, Andreas F.; Mašić, Admir; Ersen, Ovidiu; Rabu, Pierre; Meier, Wolfgang; Luch, Andreas; Taubert, Andreas
2011-12-01
Peptide-modified silver nanoparticles have been coated with an erbium-doped silica layer using a method inspired by silica biomineralization. Electron microscopy and small-angle X-ray scattering confirm the presence of an Ag/peptide core and silica shell. The erbium is present as small Er2O3 particles in and on the silica shell. Raman, IR, UV-Vis, and circular dichroism spectroscopies show that the peptide is still present after shell formation and the nanoparticles conserve a chiral plasmon resonance. Magnetic measurements find a paramagnetic behavior. In vitro tests using a macrophage cell line model show that the resulting multicomponent nanoparticles have a low toxicity for macrophages, even on partial dissolution of the silica shell.Peptide-modified silver nanoparticles have been coated with an erbium-doped silica layer using a method inspired by silica biomineralization. Electron microscopy and small-angle X-ray scattering confirm the presence of an Ag/peptide core and silica shell. The erbium is present as small Er2O3 particles in and on the silica shell. Raman, IR, UV-Vis, and circular dichroism spectroscopies show that the peptide is still present after shell formation and the nanoparticles conserve a chiral plasmon resonance. Magnetic measurements find a paramagnetic behavior. In vitro tests using a macrophage cell line model show that the resulting multicomponent nanoparticles have a low toxicity for macrophages, even on partial dissolution of the silica shell. Electronic supplementary information (ESI) available: Figures S1 to S12, Tables S1 and S2. See DOI: 10.1039/c1nr10930h
NASA Astrophysics Data System (ADS)
Ximendes, Erving Clayton; Rocha, Uéslen; Kumar, Kagola Upendra; Jacinto, Carlos; Jaque, Daniel
2016-06-01
We report on Ytterbium and Neodymium codoped LaF3 core/shell nanoparticles capable of simultaneous heating and thermal sensing under single beam infrared laser excitation. Efficient light-to-heat conversion is produced at the Neodymium highly doped shell due to non-radiative de-excitations. Thermal sensing is provided by the temperature dependent Nd3+ → Yb3+ energy transfer processes taking place at the core/shell interface. The potential application of these core/shell multifunctional nanoparticles for controlled photothermal subcutaneous treatments is also demonstrated.
Scintillation of rare earth doped fluoride nanoparticles
NASA Astrophysics Data System (ADS)
Jacobsohn, L. G.; McPherson, C. L.; Sprinkle, K. B.; Yukihara, E. G.; DeVol, T. A.; Ballato, J.
2011-09-01
The scintillation response of rare earth (RE) doped core/undoped (multi-)shell fluoride nanoparticles was investigated under x-ray and alpha particle irradiation. A significant enhancement of the scintillation response was observed with increasing shells due: (i) to the passivation of surface quenching defects together with the activation of the REs on the surface of the core nanoparticle after the growth of a shell, and (ii) to the increase of the volume of the nanoparticles. These results are expected to reflect a general aspect of the scintillation process in nanoparticles, and to impact radiation sensing technologies that make use of nanoparticles.
Can para-aryl-dithiols cross-link two plasmonic noble nanoparticles as monolayer dithiolate spacers
USDA-ARS?s Scientific Manuscript database
Para-aryl-dithiols (PADTs, HS-(C6H4)n-SH, n = 1, 2, and 3) have been used extensively in molecular electronics, surface-enhanced Raman spectroscopy (SERS), and quantum electron tunneling between two gold or silver nanoparticles (AuNPs and AgNPs). One popular belief is that these dithiols cross-link ...
Connecting quantum dots and bionanoparticles in hybrid nanoscale ultra-thin films
NASA Astrophysics Data System (ADS)
Tangirala, Ravisubhash; Hu, Yunxia; Zhang, Qingling; He, Jinbo; Russell, Thomas; Emrick, Todd
2008-03-01
Aldehyde-functionalized CdSe quantum dots and nanorods, and horse spleen ferritin bionanoparticles, were co-assembled at an oil-water interface. Reaction of the aldehydes with the surface-available amines on the ferritin particles enabled cross-linking at the interface, converting the assembled nanoparticles into robust ultra-thin films. The cross-linked capsules and sheets thus made by aldehyde-amine conjugation could be disrupted by addition of acid. Reductive amination chemistry could be performed to convert these degradable capsules and sheets into structures with irreversible cross-linking. Fluorescence confocal microscopy, scanning force microscopy and pendant drop tensiometry were used to characterize these hybrid nanoparticle-based materials, and transmission electron microscopy (TEM) confirmed the presence of both the synthetic and naturally derived nanoparticles.
Ni3Si(Al)/a-SiOx core shell nanoparticles: characterization, shell formation, and stability
NASA Astrophysics Data System (ADS)
Pigozzi, G.; Mukherji, D.; Gilles, R.; Barbier, B.; Kostorz, G.
2006-08-01
We have used an electrochemical selective phase dissolution method to extract nanoprecipitates of the Ni3Si-type intermetallic phase from two-phase Ni-Si and Ni-Si-Al alloys by dissolving the matrix phase. The extracted nanoparticles are characterized by transmission electron microscopy, energy-dispersive x-ray spectrometry, x-ray powder diffraction, and electron powder diffraction. It is found that the Ni3Si-type nanoparticles have a core-shell structure. The core maintains the size, the shape, and the crystal structure of the precipitates that existed in the bulk alloys, while the shell is an amorphous phase, containing only Si and O (SiOx). The shell forms around the precipitates during the extraction process. After annealing the nanoparticles in nitrogen at 700 °C, the tridymite phase recrystallizes within the shell, which remains partially amorphous. In contrast, on annealing in air at 1000 °C, no changes in the composition or the structure of the nanoparticles occur. It is suggested that the shell forms after dealloying of the matrix phase, where Si atoms, the main constituents of the shell, migrate to the surface of the precipitates.
Ni(3)Si(Al)/a-SiO(x) core-shell nanoparticles: characterization, shell formation, and stability.
Pigozzi, G; Mukherji, D; Gilles, R; Barbier, B; Kostorz, G
2006-08-28
We have used an electrochemical selective phase dissolution method to extract nanoprecipitates of the Ni(3)Si-type intermetallic phase from two-phase Ni-Si and Ni-Si-Al alloys by dissolving the matrix phase. The extracted nanoparticles are characterized by transmission electron microscopy, energy-dispersive x-ray spectrometry, x-ray powder diffraction, and electron powder diffraction. It is found that the Ni(3)Si-type nanoparticles have a core-shell structure. The core maintains the size, the shape, and the crystal structure of the precipitates that existed in the bulk alloys, while the shell is an amorphous phase, containing only Si and O (SiO(x)). The shell forms around the precipitates during the extraction process. After annealing the nanoparticles in nitrogen at 700 °C, the tridymite phase recrystallizes within the shell, which remains partially amorphous. In contrast, on annealing in air at 1000 °C, no changes in the composition or the structure of the nanoparticles occur. It is suggested that the shell forms after dealloying of the matrix phase, where Si atoms, the main constituents of the shell, migrate to the surface of the precipitates.
NASA Astrophysics Data System (ADS)
Manciu, Felicia Speranta
The prospects for realizing efficient nanoparticle light emitters in the visible/near IR for communications and bio-medical applications have benefited from progress in chemical fabrication of nanoparticles. III-V semiconductor nanopaticles such as GaP and InP are promising materials for the development of "blue" and "green" emitters, respectively, due to their large effective bandgaps. Enhanced emission efficiency has been achieved for core-shell nanoparticles, since inorganic shell materials increase electronic tunability and may decrease surface defects that often occur for nanoparticles capped with organic molecules. Also, the emission wavelength of InP nanoparticle cores can be tuned from green to red by changing the shell material in InP/II-VI core-shell nanoparticles. Investigations of phonon modes in nanocrystals are of both fundamental and applied interest. In the former case the optical phonon modes, such as surface/interface modes, are dependent on the nanoparticle dimensions, and also can provide information about dynamical properties of the nanoparticles and test the validity of various theoretical approaches. In the latter case the vibronic properties of nanoparticle emitters are controlled by confined phonons and modifications of the electron-phonon interaction by the confinement. Thus, the objective of the present thesis is the detailed study of the phonon modes of III-V nanoparticles (GaP and InP) and InP/II-VI core-shell nanoparticles by IR absorption and Raman scattering spectroscopies, and an elucidation of their complex vibrational properties. With the exception of three samples (two GaP and one InP), all samples were synthesized by a novel colloidal chemistry method, which does not requires added surfactant, but rather treatment of the corresponding precursors in octadecene noncoordinative solvent. Sample quality was characterized by ED, TEM and X-ray diffraction. Based on a comparison with a dielectric continuum model, the observed features in the IR and Raman results are assigned to the surface optical (SO) modes of the corresponding nanoparticles (InP and GaP), and to SO/interface modes for InP/II-VI core-shell nanoparticles. For the latter systems, an evaluation of the ratio of the shell material thickness to the core radius is achieved. Reasonable agreement is obtained between the Raman and FIR results, as well as with the calculations. (Abstract shortened by UMI.)
NASA Astrophysics Data System (ADS)
Liu, Baocang; Wang, Qin; Yu, Shengli; Jing, Peng; Liu, Lixia; Xu, Guangran; Zhang, Jun
2014-09-01
Rational design of the hierarchical architecture of a material with well controlled functionality is crucially important for improving its properties. In this paper, we present the general strategies for rationally designing and constructing three types of hierarchical Pd integrated TiO2 double-shell architectures, i.e. yolk-double-shell TiO2 architecture (Pd@TiO2/Pd@TiO2) with yolk-type Pd nanoparticles residing inside the central cavity of the hollow TiO2 structure; ultrafine Pd nanoparticles homogenously dispersed on both the external and internal surfaces of the inner TiO2 shell; and double-shell TiO2 architecture (@TiO2/Pd@TiO2) with Pd nanoparticles solely loaded on the external surface of the inner TiO2 shell, and double-shell TiO2 architecture (@TiO2@Pd@TiO2) with Pd nanoparticles dispersed in the interlayer space of double TiO2 shells, via newly developed Pd2+ ion-diffusion and Pd sol impregnation methodologies. These architectures are well controlled in structure, size, morphology, and configuration with Pd nanoparticles existing in various locations. Owing to the variable synergistic effects arising from the location discrepancies of Pd nanoparticle in the architectures, they exhibit remarkable variations in catalytic activity. In particular, different from previously reported yolk-shell structures, the obtained yolk-double-shell Pd@TiO2/Pd@TiO2 architecture, which is revealed for the first time, possesses a uniform hierarchical structure, narrow size distribution, and good monodispersibility, and it creates two Pd-TiO2 interfaces on the external and internal surfaces of the inner TiO2 shell, leading to the strongest synergistic effect of Pd nanoparticles with TiO2 shell. Furthermore, the interlayer chamber between the double TiO2 shells connecting with the central cavity of the hollow TiO2 structure through the mesoporous TiO2 wall forms a nanoreactor for enriching the reactants and preventing the deletion of Pd nanoparticles during the reaction, thus greatly accelerating the reaction speed. Owing to its structural features, yolk-double-shell Pd@TiO2/Pd@TiO2 architecture exhibits extremely high catalytic performance on the Suzuki-Miyaura coupling reaction. The synthetic methodologies are robust for fabricating double-shell architectures with various configurations for applications such as in catalysis, drug delivery, and medicine release. The obtained double-shell architectures may be used as novel catalyst systems with highly efficient catalytic performance for other catalytic reactions.Rational design of the hierarchical architecture of a material with well controlled functionality is crucially important for improving its properties. In this paper, we present the general strategies for rationally designing and constructing three types of hierarchical Pd integrated TiO2 double-shell architectures, i.e. yolk-double-shell TiO2 architecture (Pd@TiO2/Pd@TiO2) with yolk-type Pd nanoparticles residing inside the central cavity of the hollow TiO2 structure; ultrafine Pd nanoparticles homogenously dispersed on both the external and internal surfaces of the inner TiO2 shell; and double-shell TiO2 architecture (@TiO2/Pd@TiO2) with Pd nanoparticles solely loaded on the external surface of the inner TiO2 shell, and double-shell TiO2 architecture (@TiO2@Pd@TiO2) with Pd nanoparticles dispersed in the interlayer space of double TiO2 shells, via newly developed Pd2+ ion-diffusion and Pd sol impregnation methodologies. These architectures are well controlled in structure, size, morphology, and configuration with Pd nanoparticles existing in various locations. Owing to the variable synergistic effects arising from the location discrepancies of Pd nanoparticle in the architectures, they exhibit remarkable variations in catalytic activity. In particular, different from previously reported yolk-shell structures, the obtained yolk-double-shell Pd@TiO2/Pd@TiO2 architecture, which is revealed for the first time, possesses a uniform hierarchical structure, narrow size distribution, and good monodispersibility, and it creates two Pd-TiO2 interfaces on the external and internal surfaces of the inner TiO2 shell, leading to the strongest synergistic effect of Pd nanoparticles with TiO2 shell. Furthermore, the interlayer chamber between the double TiO2 shells connecting with the central cavity of the hollow TiO2 structure through the mesoporous TiO2 wall forms a nanoreactor for enriching the reactants and preventing the deletion of Pd nanoparticles during the reaction, thus greatly accelerating the reaction speed. Owing to its structural features, yolk-double-shell Pd@TiO2/Pd@TiO2 architecture exhibits extremely high catalytic performance on the Suzuki-Miyaura coupling reaction. The synthetic methodologies are robust for fabricating double-shell architectures with various configurations for applications such as in catalysis, drug delivery, and medicine release. The obtained double-shell architectures may be used as novel catalyst systems with highly efficient catalytic performance for other catalytic reactions. Electronic supplementary information (ESI) available: Synthetic schemes, TEM, SEM, XRD, FTIR, UV-DRS spectra, TPR, and catalytic data. See DOI: 10.1039/c4nr02692f
NASA Astrophysics Data System (ADS)
Patel, Sanjay K. S.; Choi, Seung Ho; Kang, Yun Chan; Lee, Jung-Kul
2016-03-01
Multiple-shelled Fe2O3 yolk-shell particles were synthesized using the spray drying method and intended as a suitable support for the immobilization of commercial enzymes such as glucose oxidase (GOx), horseradish peroxidase (HRP), and laccase as model enzymes. Yolk-shell particles have an average diameter of 1-3 μm with pore diameters in the range of 16 to 28 nm. The maximum immobilization of GOx, HRP, and laccase resulted in the enzyme loading of 292, 307 and 398 mg per g of support, respectively. After cross-linking of immobilized laccase by glutaraldehyde, immobilization efficiency was improved from 83.5% to 90.2%. Km and Vmax values were 41.5 μM and 1722 μmol min-1 per mg protein for cross-linked laccase and those for free laccase were 29.3 μM and 1890 μmol min-1 per mg protein, respectively. The thermal stability of the enzyme was enhanced up to 18-fold upon cross-linking, and the enzyme retained 93.1% of residual activity after ten cycles of reuse. The immobilized enzyme has shown up to 32-fold higher stability than the free enzyme towards different solvents and it showed higher efficiency than free laccase in the decolorization of dyes and degradation of bisphenol A. The synthesized yolk-shell particles have 3-fold higher enzyme loading efficiency and lower acute toxicity than the commercial Fe2O3 spherical particles. Therefore, the use of unique yolk-shell structure Fe2O3 particles with multiple-shells will be promising for the immobilization of various enzymes in biotechnological applications with improved electrochemical properties. To the best of our knowledge, this is the first report on the use of one pot synthesized Fe2O3 yolk-shell structure particles for the immobilization of enzymes.Multiple-shelled Fe2O3 yolk-shell particles were synthesized using the spray drying method and intended as a suitable support for the immobilization of commercial enzymes such as glucose oxidase (GOx), horseradish peroxidase (HRP), and laccase as model enzymes. Yolk-shell particles have an average diameter of 1-3 μm with pore diameters in the range of 16 to 28 nm. The maximum immobilization of GOx, HRP, and laccase resulted in the enzyme loading of 292, 307 and 398 mg per g of support, respectively. After cross-linking of immobilized laccase by glutaraldehyde, immobilization efficiency was improved from 83.5% to 90.2%. Km and Vmax values were 41.5 μM and 1722 μmol min-1 per mg protein for cross-linked laccase and those for free laccase were 29.3 μM and 1890 μmol min-1 per mg protein, respectively. The thermal stability of the enzyme was enhanced up to 18-fold upon cross-linking, and the enzyme retained 93.1% of residual activity after ten cycles of reuse. The immobilized enzyme has shown up to 32-fold higher stability than the free enzyme towards different solvents and it showed higher efficiency than free laccase in the decolorization of dyes and degradation of bisphenol A. The synthesized yolk-shell particles have 3-fold higher enzyme loading efficiency and lower acute toxicity than the commercial Fe2O3 spherical particles. Therefore, the use of unique yolk-shell structure Fe2O3 particles with multiple-shells will be promising for the immobilization of various enzymes in biotechnological applications with improved electrochemical properties. To the best of our knowledge, this is the first report on the use of one pot synthesized Fe2O3 yolk-shell structure particles for the immobilization of enzymes. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr00346j
Magnetism and Mössbauer study of formation of multi-core γ -Fe2O3 nanoparticles
NASA Astrophysics Data System (ADS)
Kamali, Saeed; Bringas, Eugenio; Hah, Hien-Yoong; Bates, Brian; Johnson, Jacqueline A.; Johnson, Charles E.; Stroeve, Pieter
2018-04-01
A systematic investigation of magnetic nanoparticles and the formation of a core-shell structure, consisting of multiple maghemite (γ -Fe2O3) nanoparticles as the core and silica as the shell, has been performed using various techniques. High-resolution transmission electron microscopy clearly shows isolated maghemite nanoparticles with an average diameter of 13 nm and the formation of a core-shell structure. Low temperature Mössbauer spectroscopy reveals the presence of pure maghemite nanoparticles with all vacancies at the B-sites. Isothermal magnetization and zero-field-cooled and field-cooled measurements are used for investigating the magnetic properties of the nanoparticles. The magnetization results are in good accordance with the contents of the magnetic core and the non-magnetic shell. The multiple-core γ -Fe2O3 nanoparticles show similar behavior to isolated particles of the same size.
Single-step generation of metal-plasma polymer multicore@shell nanoparticles from the gas phase.
Solař, Pavel; Polonskyi, Oleksandr; Olbricht, Ansgar; Hinz, Alexander; Shelemin, Artem; Kylián, Ondřej; Choukourov, Andrei; Faupel, Franz; Biederman, Hynek
2017-08-17
Nanoparticles composed of multiple silver cores and a plasma polymer shell (multicore@shell) were prepared in a single step with a gas aggregation cluster source operating with Ar/hexamethyldisiloxane mixtures and optionally oxygen. The size distribution of the metal inclusions as well as the chemical composition and the thickness of the shells were found to be controlled by the composition of the working gas mixture. Shell matrices ranging from organosilicon plasma polymer to nearly stoichiometric SiO 2 were obtained. The method allows facile fabrication of multicore@shell nanoparticles with tailored functional properties, as demonstrated here with the optical response.
Enzyme immobilization in novel alginate-chitosan core-shell microcapsules.
Taqieddin, Ehab; Amiji, Mansoor
2004-05-01
Alginate-chitosan core-shell microcapsules were prepared in order to develop a biocompatible matrix for enzyme immobilization, where the protein is retained either in a liquid or solid core and the shell allows permeability control over substrates and products. The permeability coefficients of different molecular weight compounds (vitamin B2, vitamin B12, and myoglobin) were determined through sodium tripolyphosphate (Na-TPP)-crosslinked chitosan membrane. The microcapsule core was formed by crosslinking sodium alginate with either calcium or barium ions. The crosslinked alginate core was uniformly coated with a chitosan layer and crosslinked with Na-TPP. In the case of calcium alginate, the phosphate ions of Na-TPP were able to extract the calcium ions from alginate and liquefy the core. A model enzyme, beta-galactosidase, was immobilized in the alginate core and the catalytic activity was measured with o-nitrophenyl-beta-D-galactopyranoside (ONPG). Change in the activity of free and immobilized enzyme was determined at three different temperatures. Na-TPP crosslinked chitosan membranes were found to be permeable to solutes of up to 17,000Da molecular weight. The enzyme loading efficiency was higher in the barium alginate core (100%) as compared to the calcium alginate core (60%). The rate of ONPG conversion to o-nitrophenol was faster in the case of calcium alginate-chitosan microcapsules as compared to barium alginate-chitosan microcapsules. Barium alginate-chitosan microcapsules, however, did improve the stability of the enzyme at 37 degrees C relative to calcium alginate-chitosan microcapsules or free enzyme. This study illustrates a new method of enzyme immobilization for biotechnology applications using liquid or solid core and shell microcapsule technology.
NASA Astrophysics Data System (ADS)
Mott, Derrick; Lee, JaeDong; Thi Bich Thuy, Nguyen; Aoki, Yoshiya; Singh, Prerna; Maenosono, Shinya
2011-06-01
This paper reports a qualitative comparison between the optical properties of a set of silver core, gold shell nanoparticles with varying composition and structure to those calculated using the Mie solution. To achieve this, silver nanoparticles were synthesized in aqueous phase from a silver hydroxide precursor with sodium acrylate as dual reducing-capping agent. The particles were then coated with a layer of gold with controllable thickness through a reduction-deposition process. The resulting nanoparticles reveal well defined optical properties that make them suitable for comparison to ideal calculated results using the Mie solution. The discussion focuses on the correlation between the synthesized core shell nanoparticles with varying Au shell thickness and the Mie solution results in terms of the optical properties. The results give insight in how to design and synthesize silver core, gold shell nanoparticles with controllable optical properties (e.g., SPR band in terms of intensity and position), and has implications in creating nanoparticle materials to be used as biological probes and sensing elements.
Zhao, Jie; Lu, Zhenda; Liu, Nian; Lee, Hyun-Wook; McDowell, Matthew T; Cui, Yi
2014-10-03
Rapid progress has been made in realizing battery electrode materials with high capacity and long-term cyclability in the past decade. However, low first-cycle Coulombic efficiency as a result of the formation of a solid electrolyte interphase and Li trapping at the anodes, remains unresolved. Here we report LixSi-Li2O core-shell nanoparticles as an excellent prelithiation reagent with high specific capacity to compensate the first-cycle capacity loss. These nanoparticles are produced via a one-step thermal alloying process. LixSi-Li2O core-shell nanoparticles are processible in a slurry and exhibit high capacity under dry-air conditions with the protection of a Li2O passivation shell, indicating that these nanoparticles are potentially compatible with industrial battery fabrication processes. Both Si and graphite anodes are successfully prelithiated with these nanoparticles to achieve high first-cycle Coulombic efficiencies of 94% to >100%. The LixSi-Li2O core-shell nanoparticles enable the practical implementation of high-performance electrode materials in lithium-ion batteries.
Liu, Baocang; Wang, Qin; Yu, Shengli; Jing, Peng; Liu, Lixia; Xu, Guangran; Zhang, Jun
2014-10-21
Rational design of the hierarchical architecture of a material with well controlled functionality is crucially important for improving its properties. In this paper, we present the general strategies for rationally designing and constructing three types of hierarchical Pd integrated TiO2 double-shell architectures, i.e. yolk-double-shell TiO2 architecture (Pd@TiO2/Pd@TiO2) with yolk-type Pd nanoparticles residing inside the central cavity of the hollow TiO2 structure; ultrafine Pd nanoparticles homogenously dispersed on both the external and internal surfaces of the inner TiO2 shell; and double-shell TiO2 architecture (@TiO2/Pd@TiO2) with Pd nanoparticles solely loaded on the external surface of the inner TiO2 shell, and double-shell TiO2 architecture (@TiO2@Pd@TiO2) with Pd nanoparticles dispersed in the interlayer space of double TiO2 shells, via newly developed Pd(2+) ion-diffusion and Pd sol impregnation methodologies. These architectures are well controlled in structure, size, morphology, and configuration with Pd nanoparticles existing in various locations. Owing to the variable synergistic effects arising from the location discrepancies of Pd nanoparticle in the architectures, they exhibit remarkable variations in catalytic activity. In particular, different from previously reported yolk-shell structures, the obtained yolk-double-shell Pd@TiO2/Pd@TiO2 architecture, which is revealed for the first time, possesses a uniform hierarchical structure, narrow size distribution, and good monodispersibility, and it creates two Pd-TiO2 interfaces on the external and internal surfaces of the inner TiO2 shell, leading to the strongest synergistic effect of Pd nanoparticles with TiO2 shell. Furthermore, the interlayer chamber between the double TiO2 shells connecting with the central cavity of the hollow TiO2 structure through the mesoporous TiO2 wall forms a nanoreactor for enriching the reactants and preventing the deletion of Pd nanoparticles during the reaction, thus greatly accelerating the reaction speed. Owing to its structural features, yolk-double-shell Pd@TiO2/Pd@TiO2 architecture exhibits extremely high catalytic performance on the Suzuki-Miyaura coupling reaction. The synthetic methodologies are robust for fabricating double-shell architectures with various configurations for applications such as in catalysis, drug delivery, and medicine release. The obtained double-shell architectures may be used as novel catalyst systems with highly efficient catalytic performance for other catalytic reactions.
NASA Astrophysics Data System (ADS)
Lee, Shih-Chi; Fu, Chao-Ming; Chang, Fu-Hsiung
2013-10-01
Fe3O4/γ-Fe2O3 core-shell magnetic nanoparticles have demonstrated superior heating efficiency by applying the alternating magnetic field. The magnetic induction heating properties of core-shell magnetic nanoparticles were analyzed by the rate-dependent hysteresis model, taken into account the magnetic anisotropies and actual size distribution of particles. The analyzed results have disclosed the significance of magnetic anisotropies and shell-thickness to the promotion of magnetic induction heating performance. Further experiments about the cancer cells with uptake of these core-shell magnetic nanoparticles conjugated biocompatible cationic liposomes have achieved in vitro intracellular magnetically induced hyperthermia under a weak alternating magnetic field.
Feng, Yan; Ye, Feng; Liu, Hui; Yang, Jun
2015-11-18
Mastery over the structure of nanoparticles might be an effective way to enhance their performance for a given application. Herein we demonstrate the design of cage-bell nanostructures to enhance the methanol tolerance of platinum (Pt) nanoparticles while remaining their catalytic activity for oxygen reduction reaction. This strategy starts with the synthesis of core-shell-shell nanoparticles with Pt and silver (Ag) residing respectively in the core and inner shell regions, which are then agitated with saturated sodium chloride (NaCl) solution to eliminate the Ag component from the inner shell region, leading to the formation of bimetallic nanoparticles with a cage-bell structure, defined as a movable Pt core enclosed by a metal shell with nano-channels, which exhibit superior methanol-tolerant property in catalyzing oxygen reduction reaction due to the different diffusion behaviour of methanol and oxygen in the porous metal shell of cage-bell structured nanoparticles. In particular, the use of remarkably inexpensive chemical agent (NaCl) to promote the formation of cage-bell structured particles containing a wide spectrum of metal shells highlights its engineering merit to produce highly selective electrocatalysts on a large scale for the cathode reaction of direct methanol fuel cells.
A pathway for the growth of core-shell Pt-Pd nanoparticles
Narula, Chaitanya Kumar; Yang, Xiaofan; Li, Chen; ...
2015-10-12
In this study, the aging of both Pt-Pd nanoparticles and core-shell Pt-Pd nanoparticles has been reported to result in alloying of Pt with Pd. In comparison to monometallic Pt catalysts, the growth of Pd-Pt bimetallics is slower; however, the mechanism of growth of particles and the mechanism by which Pd improves the hydrothermal durability of bimetallic Pd-Pt particles remains uncertain. In our work on hydrothermal aging of core-shell Pt-Pd nanoparticles, synthesized by solution methods, with varying Pd:Pt ratio of 1:4, 1:1, and 4:1, we compare the growth of core-shell Pt-Pd nanoparticles and find that particles grow by migrating and joiningmore » together. The unique feature of the observed growth is that Pd shells from both particles open up and join, allowing the cores to merge. At high temperatures, alloying occurs in good agreement with reports by other workers.« less
Lim, Joohyun; Um, Ji Hyun; Ahn, Jihoon; Yu, Seung-Ho; Sung, Yung-Eun; Lee, Jin-Kyu
2015-05-18
Yolk-shell-structured nanoparticles with iron oxide core, void, and a titania shell configuration are prepared by a simple soft template method and used as the anode material for lithium ion batteries. The iron oxide-titania yolk-shell nanoparticles (IO@void@TNPs) exhibit a higher and more stable capacity than simply mixed nanoparticles of iron oxide and hollow titania because of the unique structure obtained by the perfect separation between iron oxide nanoparticles, in combination with the adequate internal void space provided by stable titania shells. Moreover, the structural effect of IO@void@TNPs clearly demonstrates that the capacity retention value after 50 cycles is approximately 4 times that for IONPs under harsh operating conditions, that is, when the temperature is increased to 80 °C. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Jaramillo, Johny; Boudouris, Bryan W; Barrero, César A; Jaramillo, Franklin
2015-11-18
Controlling the nature and transfer of excited states in organic photovoltaic (OPV) devices is of critical concern due to the fact that exciton transport and separation can dictate the final performance of the system. One effective method to accomplish improved charge separation in organic electronic materials is to control the spin state of the photogenerated charge-carrying species. To this end, nanoparticles with unique iron oxide (Fe3O4) cores and zinc oxide (ZnO) shells were synthesized in a controlled manner. Then, the structural and magnetic properties of these core-shell nanoparticles (Fe3O4@ZnO) were tuned to ensure superior performance when they were incorporated into the active layers of OPV devices. Specifically, small loadings of the core-shell nanoparticles were blended with the previously well-characterized OPV active layer of poly(3-hexylthiophene) (P3HT) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM). Upon addition of the core-shell nanoparticles, the performance of the OPV devices was increased up to 25% relative to P3HT-PCBM active layer devices that contained no nanoparticles; this increase was a direct result of an increase in the short-circuit current densities of the devices. Furthermore, it was demonstrated that the increase in photocurrent was not due to enhanced absorption of the active layer due to the presence of the Fe3O4@ZnO core-shell nanoparticles. In fact, this increase in device performance occurred because of the presence of the superparamagnetic Fe3O4 in the core of the nanoparticles as incorporation of ZnO only nanoparticles did not alter the device performance. Importantly, however, the ZnO shell of the nanoparticles mitigated the negative optical effect of Fe3O4, which have been observed previously. This allowed the core-shell nanoparticles to outperform bare Fe3O4 nanoparticles when the single-layer nanoparticles were incorporated into the active layer of OPV devices. As such, the new materials described here present a tangible pathway toward the development of enhanced design schemes for inorganic nanoparticles such that magnetic and energy control pathways can be tailored for flexible electronic applications.
NASA Astrophysics Data System (ADS)
Zhu, Jian; Li, Jian-Jun; Wang, A.-Qing; Chen, Yu; Zhao, Jun-Wu
2010-09-01
Fluorescence quenching spectrometry was applied to study the interactions between gold colloidal nanoparticles and alpha-fetoprotein (AFP). Experimental results show that the gold nanoparticles can quench the fluorescence emission of adsorbed AFP effectively. Furthermore, the intensity of fluorescence emission peak decreases monotonously with the increasing gold nanoparticles content. A mechanism based on surface plasmon resonance-induced non-radiative decay was investigated to illuminate the effect of a dielectric shell on the fluorescence quenching ability of gold nanoparticles. The calculation results show that the increasing dielectric shell thickness may improve the monochromaticity of fluorescence quenching. However, high energy transfer efficiency can be obtained within a wide wavelength band by coating a thinner dielectric shell.
Assembly of metals and nanoparticles into novel nanocomposite superstructures
Xu, Jiaquan; Chen, Lianyi; Choi, Hongseok; Konish, Hiromi; Li, Xiaochun
2013-01-01
Controlled assembly of nanoscale objects into superstructures is of tremendous interests. Many approaches have been developed to fabricate organic-nanoparticle superstructures. However, effective fabrication of inorganic-nanoparticle superstructures (such as nanoparticles linked by metals) remains a difficult challenge. Here we show a novel, general method to assemble metals and nanoparticles rationally into nanocomposite superstructures. Novel metal-nanoparticle superstructures are achieved by self-assembly of liquid metals and nanoparticles in immiscible liquids driven by reduction of free energy. Superstructures with various architectures, such as metal-core/nanoparticle-shell, nanocomposite-core/nanoparticle-shell, network of metal-linked core/shell nanostructures, and network of metal-linked nanoparticles, were successfully fabricated by simply tuning the volume ratio between nanoparticles and liquid metals. Our approach provides a simple, general way for fabrication of numerous metal-nanoparticle superstructures and enables a rational design of these novel superstructures with desired architectures for exciting applications.
Uzayisenga, Viviane; Lin, Xiao-Dong; Li, Li-Mei; Anema, Jason R; Yang, Zhi-Lin; Huang, Yi-Fan; Lin, Hai-Xin; Li, Song-Bo; Li, Jian-Feng; Tian, Zhong-Qun
2012-06-19
Au-seed Ag-growth nanoparticles of controllable diameter (50-100 nm), and having an ultrathin SiO(2) shell of controllable thickness (2-3 nm), were prepared for shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). Their morphological, optical, and material properties were characterized; and their potential for use as a versatile Raman signal amplifier was investigated experimentally using pyridine as a probe molecule and theoretically by the three-dimensional finite-difference time-domain (3D-FDTD) method. We show that a SiO(2) shell as thin as 2 nm can be synthesized pinhole-free on the Ag surface of a nanoparticle, which then becomes the core. The dielectric SiO(2) shell serves to isolate the Raman-signal enhancing core and prevent it from interfering with the system under study. The SiO(2) shell also hinders oxidation of the Ag surface and nanoparticle aggregation. It significantly improves the stability and reproducibility of surface-enhanced Raman scattering (SERS) signal intensity, which is essential for SERS applications. Our 3D-FDTD simulations show that Ag-core SHINERS nanoparticles yield at least 2 orders of magnitude greater enhancement than Au-core ones when excited with green light on a smooth Ag surface, and thus add to the versatility of our SHINERS method.
Chen, Qijing; Cao, Xueteng; Xu, Yuanyuan; An, Zesheng
2013-10-01
Core cross-linked star (CCS) polymers become increasingly important in polymer science and are evaluated in many value-added applications. However, limitations exist to varied degrees for different synthetic methods. It is clear that improvement in synthetic efficiency is fundamental in driving this field moving even further. Here, the most recent advances are highlighted in synthetic strategies, including cross-linking with cross-linkers of low solubility, polymerization-induced self-assembly in aqueous-based heterogeneous media, and cross-linking via dynamic covalent bonds. The understanding of CCS polymers is also further refined to advocate their role as an intermediate between linear polymers and polymeric nanoparticles, and their use as interfacial stabilizers is rationalized within this context. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Chen, Xin; Zhou, Junwei; Chen, Shuangjing; Zhang, Hui
2018-06-01
To reduce the use of precious metals and maintain the catalytic activity for NH3 decomposition reaction, it is an effective way to construct bimetallic nanoparticles with special structures. In this paper, by using density functional theory methods, we investigated NH3 decomposition reaction on three types of core-shell nanoparticles M@Ni (M = Fe, Ru, Ir) with 13 core M atoms and 42 shell Ni atoms. The size of these three particles is about 1 nm. Benefit from alloying with Ru in this nanocluster, Ru@Ni core-shell nanoparticles exhibit catalytic activity comparable to that of single metal Ru, based on the analysis of the adsorption energy and potential energy diagram of NH3 decomposition, as well as N2 desorption processes. However, as for Fe@Ni and Ir@Ni core-shell nanoparticles, their catalytic activities are still unsatisfactory compared to the active metal Ru. In addition, in order to further explain the synergistic effect of bimetallic core-shell nanoparticles, the partial density of states were also calculated. The results show that d-band electrons provided by the core metal are the main factors affecting the entire catalytic process.
NASA Astrophysics Data System (ADS)
Pukhov, Konstantin K.
2017-12-01
Here we discuss the radiative decays of excited states of transition elements located inside and outside of the subwavelength core-shell nanoparticles embedded in dielectric medium. Based on the quantum mechanics and quantum electrodynamics, the general analytical expressions are derived for the probability of the spontaneous transitions in the luminescent centers (emitter) inside and outside the subwavelength core-shell nanoparticle. Obtained expressions holds for arbitrary orientation of the dipole moment and the principal axes of the quadrupole moment of the emitter with respect to the radius-vector r connecting the center of the emitter with the center of the nanoparticle. They have simple form and show how the spontaneous emission in core-shell NPs can be controlled and engineered due to the dependence of the emission rates on core-shell sizes, radius-vector r and permittivities of the surrounding medium, shell, and core.
NASA Astrophysics Data System (ADS)
Riasat, Rabia; Kaynat, Sumbal
2018-04-01
Iron oxide nanoparticles have gained attention recently in the field of nanoscience and technology due to their unique physicochemical properties. We hereby chemically synthesized novel pentagonal flower shaped iron oxide nanoparticles by thermal decomposition of iron penta-carbonyl in a two way annealing process. Controlled oxidation by acid etching was performed for these nanoparticles. At first 13 nm core shell nanoparticles of iron oxide (Fe/Fe3O4) were synthesized at 120°C annealing temperature that act as template material. The core shell nanoparticles then converted into porous hollow core shell nanoparticles (PH Fe/ Fe3O4) in a two way annealing process of heating, first at 100°C then at 250°C and heating rate of 5°C was kept constant throughout the reaction time. X-Ray diffraction (XRD) was done for the phase confirmation of as synthesized nanoparticles. Transmission electron microscopy (TEM) and higher resolution transmission electron microscopy (HRTEM) clearly shows the flower like nanoparticles that are approx. 16 nm-18 nm in size having the 4-5 nm core of Fe and 1-2 nm of the pores in the shell while the cavity between the shell and core is about 2 nm and the shell is 4-5 nm in diameter according to the TEM micrographs. The as prepared nanoparticles were then surface functionalized by dopamine polymer to make them water dispersible. Fourier transform Infrared spectroscopy confirmed the dopamine coating on the nanoparticles and the magnetic saturation of 38 emu/g of nanoparticles was analyzed by vibrating sample magnetometer (VSM). Magnetic saturation persists in the dopamine coated nanoparticles. These nanoparticles were surface functionalized with dopamine and show dispersity in the aqueous media and can further be exploited in many nano-biotechnological applications including target specific therapeutic applications for several diseases.
Yoo, Youngman; Martinez, Carlos; Youngblood, Jeffrey P
2017-09-20
The main objective of this study is to develop microencapsulation technology for thermal energy storage incorporating a phase change material (PCM) in a composite wall shell, which can be used to create a stable environment and allow the PCM to undergo phase change without any outside influence. Surface modification of cellulose nanocrystals (CNCs) was conducted by grafting poly(lactic acid) oligomers and oleic acid to improve the dispersion of nanoparticles in a polymeric shell. A microencapsulated phase change material (methyl laurate) with poly(urea-urethane) (PU) composite shells containing the hydrophobized cellulose nanocrystals (hCNCs) was fabricated using an in situ emulsion interfacial polymerization process. The encapsulation process of the PCMs with subsequent interfacial hCNC-PU to form composite microcapsules as well as their morphology, composition, thermal properties, and release rates was examined in this study. Oil soluble Sudan II dye solution in methyl laurate was used as a model hydrophobic fill, representing other latent fills with low partition coefficients, and their encapsulation efficiency as well as dye release rates were measured spectroscopically in a water medium. The influence of polyol content in the PU polymer matrix of microcapsules was investigated. An increase in polyol contents leads to an increase in the mean size of microcapsules but a decrease in the gel content (degree of cross-linking density) and permeability of their shell structure. The encapsulated PCMs for thermal energy storage demonstrated here exhibited promising performance for possible use in building or paving materials in terms of released heat, desired phase transformation temperature, chemical and physical stability, and concrete durability during placement.
Gold nanoparticle capture within protein crystal scaffolds.
Kowalski, Ann E; Huber, Thaddaus R; Ni, Thomas W; Hartje, Luke F; Appel, Karina L; Yost, Jarad W; Ackerson, Christopher J; Snow, Christopher D
2016-07-07
DNA assemblies have been used to organize inorganic nanoparticles into 3D arrays, with emergent properties arising as a result of nanoparticle spacing and geometry. We report here the use of engineered protein crystals as an alternative approach to biologically mediated assembly of inorganic nanoparticles. The protein crystal's 13 nm diameter pores result in an 80% solvent content and display hexahistidine sequences on their interior. The hexahistidine sequence captures Au25(glutathione)∼17 (nitrilotriacetic acid)∼1 nanoclusters throughout a chemically crosslinked crystal via the coordination of Ni(ii) to both the cluster and the protein. Nanoparticle loading was validated by confocal microscopy and elemental analysis. The nanoparticles may be released from the crystal by exposure to EDTA, which chelates the Ni(ii) and breaks the specific protein/nanoparticle interaction. The integrity of the protein crystals after crosslinking and nanoparticle capture was confirmed by single crystal X-ray crystallography.
Large patternable metal nanoparticle sheets by photo/e-beam lithography
NASA Astrophysics Data System (ADS)
Saito, Noboru; Wang, Pangpang; Okamoto, Koichi; Ryuzaki, Sou; Tamada, Kaoru
2017-10-01
Techniques for micro/nano-scale patterning of large metal nanoparticle sheets can potentially be used to realize high-performance photoelectronic devices because the sheets provide greatly enhanced electrical fields around the nanoparticles due to localized surface plasmon resonances. However, no single metal nanoparticle sheet currently exists with sufficient durability for conventional lithographical processes. Here, we report large photo and/or e-beam lithographic patternable metal nanoparticle sheets with improved durability by incorporating molecular cross-linked structures between nanoparticles. The cross-linked structures were easily formed by a one-step chemical reaction; immersing a single nanoparticle sheet consisting of core metals, to which capping molecules ionically bond, in a dithiol ethanol solution. The ligand exchange reaction processes were discussed in detail, and we demonstrated 20 μm wide line and space patterns, and a 170 nm wide line of the silver nanoparticle sheets.
NASA Astrophysics Data System (ADS)
Huang, Shuangshuang; Yang, Nating; Wang, Shibin; Sun, Yuhan; Zhu, Yan
2016-07-01
Pt-Cu nanoparticles constructed with a hollow core and porous shell have been synthesized in which Pt-Cu cages with multiporous outermost shells are formed at the initial stage and then the Pt and Cu atoms in solution continuously fed these hollow-core of cages by passing through the porous tunnels of the outermost shells, finally leading to the formation of hollow structures with different sizes. Furthermore, these hollow-core Pt-Cu nanoparticles are more effective than the solid-core Pt-Cu nanoparticles for the catalytic hydrogenation of furfural toward furfuryl alcohol. The former can achieve almost 100% conversion of furfural with 100% selectivity toward the alcohol.Pt-Cu nanoparticles constructed with a hollow core and porous shell have been synthesized in which Pt-Cu cages with multiporous outermost shells are formed at the initial stage and then the Pt and Cu atoms in solution continuously fed these hollow-core of cages by passing through the porous tunnels of the outermost shells, finally leading to the formation of hollow structures with different sizes. Furthermore, these hollow-core Pt-Cu nanoparticles are more effective than the solid-core Pt-Cu nanoparticles for the catalytic hydrogenation of furfural toward furfuryl alcohol. The former can achieve almost 100% conversion of furfural with 100% selectivity toward the alcohol. Electronic supplementary information (ESI) available. See DOI: 10.1039/c6nr03894h
Chen, Guangyu; Kuttiyiel, Kurian A.; Su, Dong; ...
2016-07-12
Here, we describe pronounced effects of structural changes of the AuNi cores on the oxygen reduction reaction (ORR) activity of a Pt monolayer shell. The study of alloyed AuNi nanoparticles compared with AuNi core–shell structured nanoparticles revealed configurations having different electronic and electrochemical properties. Controlled alloying of Au with Ni was essential to tune the electronic properties of Au interacting with the Pt monolayer shell to achieve suitable adsorption of O 2 on Pt for expediting the ORR. The alloyed AuNi nanoparticles made the Pt shell more catalytically active for the ORR than the core–shell structured AuNi nanoparticles. The Ptmore » monolayer supported on the alloyed AuNi nanoparticles showed the Pt mass and specific activities as high as 1.52 A mg –1 and 1.18 mA cm –2, respectively, with almost no loss over 5 000 cycles of stability test. This high ORR activity is ascribed to the role of nonspecific steric configuration of Ni atoms changing the electronic properties of the alloy that affect the oxygen and water interaction with the Pt shell and facilitate increased ORR kinetics.« less
Liquid-Crystalline Elastomers with Gold Nanoparticle Cross-Linkers.
Wójcik, Michał M; Wróbel, Jarosław; Jańczuk, Zuzanna Z; Mieczkowski, Józef; Górecka, Ewa; Choi, Joonmyung; Cho, Maenghyo; Pociecha, Damian
2017-07-03
Embedding nanoparticles in a responsive polymer matrix is a formidable way to fabricate hybrid materials with predesigned properties and prospective applications in actuators, mechanically tunable optical elements, and electroclinic films. However, achieving chemical compatibility between nanoparticles and organic matter is not trivial and often results in disordered structures. Herein, it is shown that using nanoparticles as exclusive cross-linkers in the preparation of liquid-crystalline polymers can yield long-range-ordered liquid-crystalline elastomers with high loadings of well-dispersed nanoparticles, as confirmed by small-angle XRD measurements. Moreover, the strategy of incorporating NPs as cross-linking units does not result in disruption of mechanical properties of the polymer, and this phenomenon was explained by the means of all-atom molecular dynamics simulations. Such materials can exhibit switchable behavior under thermal stimulus with stability spanning over multiple heating/cooling cycles. The presented strategy has proven to be a promising approach for the preparation of new types of hybrid liquid-crystalline elastomers that can be of value for future photonic applications. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won
2016-01-01
Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842
Morphology and electronic structure of the oxide shell on the surface of iron nanoparticles.
Wang, Chongmin; Baer, Donald R; Amonette, James E; Engelhard, Mark H; Antony, Jiji; Qiang, You
2009-07-01
An iron (Fe) nanoparticle exposed to air at room temperature will be instantly covered by an oxide shell that is typically approximately 3 nm thick. The nature of this native oxide shell, in combination with the underlying Fe(0) core, determines the physical and chemical behavior of the core-shell nanoparticle. One of the challenges of characterizing core-shell nanoparticles is determining the structure of the oxide shell, that is, whether it is FeO, Fe(3)O(4), gamma-Fe(2)O(3), alpha-Fe(2)O(3), or something else. The results of prior characterization efforts, which have mostly used X-ray diffraction and spectroscopy, electron diffraction, and transmission electron microscopic imaging, have been framed in terms of one of the known Fe-oxide structures, although it is not necessarily true that the thin layer of Fe oxide is a known Fe oxide. In this Article, we probe the structure of the oxide shell on Fe nanoparticles using electron energy loss spectroscopy (EELS) at the oxygen (O) K-edge with a spatial resolution of several nanometers (i.e., less than that of an individual particle). We studied two types of representative particles: small particles that are fully oxidized (no Fe(0) core) and larger core-shell particles that possess an Fe core. We found that O K-edge spectra collected for the oxide shell in nanoparticles show distinct differences from those of known Fe oxides. Typically, the prepeak of the spectra collected on both the core-shell and the fully oxidized particles is weaker than that collected on standard Fe(3)O(4). Given the fact that the origin of this prepeak corresponds to the transition of the O 1s electron to the unoccupied state of O 2p hybridized with Fe 3d, a weak pre-edge peak indicates a combination of the following four factors: a higher degree of occupancy of the Fe 3d orbital; a longer Fe-O bond length; a decreased covalency of the Fe-O bond; and a measure of cation vacancies. These results suggest that the coordination configuration in the oxide shell on Fe nanoparticles is defective as compared to that of their bulk counterparts. Implications of these defective structural characteristics on the properties of core-shell structured iron nanoparticles are discussed.
Lam, P-L; Kok, S H-L; Bian, Z-X; Lam, K-H; Tang, J C-O; Lee, K K-H; Gambari, R; Chui, C-H
2014-05-01
Gelatin/Collagen-based matrix and reservoir nanoparticles require crosslinkers to stabilize the formed nanosuspensions, considering that physical instability is the main challenge of nanoparticulate systems. The use of crosslinkers improves the physical integrity of nanoformulations under the-host environment. Aldehyde-based fixatives, such as formaldehyde and glutaraldehyde, have been widely applied to the crosslinking process of polymeric nanoparticles. However, their potential toxicity towards human beings has been demonstrated in many previous studies. In order to tackle this problem, D-glucose was used during nanoparticle formation to stabilize the gelatin/collagen-based matrix wall and reservoir wall for the deliveries of Calendula officinalis powder and oil, respectively. In addition, therapeutic selectivity between malignant and normal cells could be observed. The C. officinalis powder loaded nanoparticles significantly strengthened the anti-cancer effect towards human breast adenocarcinoma MCF7 cells and human hepatoma SKHep1 cells when compared with the free powder. On the contrary, the nanoparticles did not show significant cytotoxicity towards normal esophageal epithelial NE3 cells and human skin keratinocyte HaCaT cells. On the basis of these evidences, D-glucose modified gelatin/collagen matrix nanoparticles containing C. officinalis powder might be proposed as a safer alternative vehicle for anti-cancer treatments. Copyright © 2014 Elsevier B.V. All rights reserved.
Adesina, Simeon K.; Wight, Scott A.; Akala, Emmanuel O.
2015-01-01
Purpose Nanoparticle size is important in drug delivery. Clearance of nanoparticles by cells of the reticuloendothelial system has been reported to increase with increase in particle size. Further, nanoparticles should be small enough to avoid lung or spleen filtering effects. Endocytosis and accumulation in tumor tissue by the enhanced permeability and retention effect are also processes that are influenced by particle size. We present the results of studies designed to optimize crosslinked biodegradable stealth polymeric nanoparticles fabricated by dispersion polymerization. Methods Nanoparticles were fabricated using different amounts of macromonomer, initiators, crosslinking agent and stabilizer in a dioxane/DMSO/water solvent system. Confirmation of nanoparticle formation was by scanning electron microscopy (SEM). Particle size was measured by dynamic light scattering (DLS). D-optimal mixture statistical experimental design was used for the experimental runs, followed by model generation (Scheffe polynomial) and optimization with the aid of a computer software. Model verification was done by comparing particle size data of some suggested solutions to the predicted particle sizes. Results and Conclusion Data showed that average particle sizes follow the same trend as predicted by the model. Negative terms in the model corresponding to the crosslinking agent and stabilizer indicate the important factors for minimizing particle size. PMID:24059281
Adesina, Simeon K; Wight, Scott A; Akala, Emmanuel O
2014-11-01
Nanoparticle size is important in drug delivery. Clearance of nanoparticles by cells of the reticuloendothelial system has been reported to increase with increase in particle size. Further, nanoparticles should be small enough to avoid lung or spleen filtering effects. Endocytosis and accumulation in tumor tissue by the enhanced permeability and retention effect are also processes that are influenced by particle size. We present the results of studies designed to optimize cross-linked biodegradable stealth polymeric nanoparticles fabricated by dispersion polymerization. Nanoparticles were fabricated using different amounts of macromonomer, initiators, crosslinking agent and stabilizer in a dioxane/DMSO/water solvent system. Confirmation of nanoparticle formation was by scanning electron microscopy (SEM). Particle size was measured by dynamic light scattering (DLS). D-optimal mixture statistical experimental design was used for the experimental runs, followed by model generation (Scheffe polynomial) and optimization with the aid of a computer software. Model verification was done by comparing particle size data of some suggested solutions to the predicted particle sizes. Data showed that average particle sizes follow the same trend as predicted by the model. Negative terms in the model corresponding to the cross-linking agent and stabilizer indicate the important factors for minimizing particle size.
NASA Astrophysics Data System (ADS)
Vanathi Vijayalakshmi, R.; Praveen Kumar, P.; Selvarani, S.; Rajakumar, P.; Ravichandran, K.
2017-10-01
A series of core@shell nanoparticles (Co@TiO2, Ag@TiO2 and Co@AgCl) stabilized with zeroth generation triazolylchalcone dendrimer was synthesized using reduction transmetalation method. The coordination of chalcone dendrimer with silver ions was confirmed by UV-vis spectroscopy. The NMR spectrum ensures the number of protons and carbon signals in the chalcone dendrimer. The prepared samples were structurally characterized by XRD, FESEM and HRTEM analysis. The SAED and XRD analyses exhibited the cubic structure with d hkl = 2.2 Å, 1.9 Å and 1.38 Å. The antibacterial and antifungal activities of the dendrimer stabilized core@shell nanoparticles (DSCSNPs) were tested against the pathogens Bacillus subtilis, Proteus mirabilis, Candida albicans and Aspergillus nigir from which it is identified that the dendrimer stabilized core shell nanoparticles with silver ions at the shell (Co@AgCl) shows effectively high activity against the tested pathogen following the other core@shell nanoparticles viz Ag@TiO2 and Co@TiO2.
McFearin, Cathryn L.; Sankaranarayanan, Jagadis; Almutairi, Adah
2011-01-01
Real Time Characterization of Protein Delivery Systems A fiber optic coupled ATR-FTIR spectroscopy technique was applied to the study of two different therapeutic delivery systems, acid degradable hydrogels and nanoparticles. Real time exponential release of a model protein, human serum albumin (HSA), was observed from two different polymeric hydrogels formulated with a pH sensitive crosslinker. Spectroscopic examination of nanoparticles formulated with an acid degradable polymer shell and encapsulated HSA exhibited vibrational signatures characteristic of both particle and payload when exposed to lowered pH conditions demonstrating the ability of this methodology to simultaneously measure phenomena arising from a system with a mixture of components. In addition, thorough characterization of these pH sensitive delivery vehicles without encapsulated protein was also accomplished in order to separate the effects of the payload during degradation. By providing in situ, real time detection in combination with the ability to specifically identify different components in a mixture without involved sample preparation and minimal sample disturbance, the versatility and suitability of this type of experiment for research in the pharmaceutical field is demonstrated. PMID:21476582
Sood, Ankur; Arora, Varun; Shah, Jyoti; Kotnala, R K; Jain, Tapan K
2017-11-01
In this paper we report synthesis of aqueous based gold coated iron oxide nanoparticles to integrate the localized surface plasma resonance (SPR) properties of gold and magnetic properties of iron oxide in a single system. Iron oxide-gold core shell nanoparticles were stabilized by attachment of thiolated sodium alginate to the surface of nanoparticles. Transmission electron microscope (TEM) micrograph presents an average elementary particle size of 8.1±2.1nm. High resolution TEM (HR-TEM) and X-ray photon spectroscopy further confirms the presence of gold shell around iron oxide core. Gold coating is responsible for reducing saturation magnetization (M s ) value from ~41emu/g to ~24emu/g - in thiolated sodium alginate stabilized gold coated iron oxide core-shell nanoparticles. The drug (curcumin) loading efficiency for the prepared nanocomposites was estimated to be around 7.2wt% (72μgdrug/mg nanoparticles) with encapsulation efficiency of 72.8%. Gold-coated iron oxide core-shell nanoparticles could be of immense importance in the field of targeted drug delivery along with capability to be used as contrast agent for MRI & CT. Copyright © 2017 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Desautels, R. D.; Freeland, J. W.; Rowe, M. P.
2015-05-07
We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO2 and Fe49%Co49%V2%/SiO2 core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, and vanadium silicates. Magnetometry experiments havemore » shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO2-based interfacial shell.« less
Feygenson, Mikhail; Formo, Eric V.; Freeman, Katherine; ...
2015-11-02
In this study, we describe how the exchange bias effect in Co/CoO nanoparticles depends on the size focusing and temperature treatment of precursor Co nanoparticles before oxidation at ambient conditions. By appealing to magnetization, microscopy, neutron and synchrotron x-ray measurements we found that as-synthesized Co nanoparticles readily oxidize in air only after 20 days. The highest exchange bias field of 814 Oe is observed at T = 2K. When the same nanoparticles are centrifuged and annealed at 70 °C in vacuum prior to oxidation, the exchange bias field is increased to 2570 Oe. Annealing of Co nanoparticles in vacuum improvesmore » their crystallinity and prevents complete oxidation, so that Co-core/CoO-shell structure is preserved even after 120 days. The crystal structure of CoO shell in both samples is different from its bulk counterpart. Implications of such distorted CoO shells on exchange bias are discussed. Coating of Co nanoparticles with amorphous silica shell makes them resistant to oxidation, but ultimately modifies the crystal structure of both Co core and SiO 2 shell.« less
Liu, Wei-Liang; Lin, Fan-Cheng; Yang, Yu-Chen; Huang, Chen-Hsien; Gwo, Shangjr; Huang, Michael H; Huang, Jer-Shing
2013-09-07
Plasmonic core-shell nanoparticles (PCSNPs) can function as nanoantennas and improve the efficiency of dye-sensitized solar cells (DSSCs). To achieve maximum enhancement, the morphology of PCSNPs needs to be optimized. Here we precisely control the morphology of Au@TiO2 PCSNPs and systematically study its influence on the plasmonic enhancement effect. The enhancement mechanism was found to vary with the thickness of the TiO2 shell. PCSNPs with a thinner shell mainly enhance the current, whereas particles with a thicker shell improve the voltage. While pronounced plasmonic enhancement was found in the near infrared regime, wavelength-independent enhancement in the visible range was observed and attributed to the plasmonic heating effect. Emission lifetime measurement confirms that N719 molecules neighboring nanoparticles with TiO2 shells exhibit a longer lifetime than those in contact with metal cores. Overall, PCSNPs with a 5 nm shell give the highest efficiency enhancement of 23%. Our work provides a new synthesis route for well-controlled Au@TiO2 core-shell nanoparticles and gains insight into the plasmonic enhancement in DSSCs.
Multi-photon excited luminescence of magnetic FePt core-shell nanoparticles.
Seemann, K M; Kuhn, B
2014-07-01
We present magnetic FePt nanoparticles with a hydrophilic, inert, and biocompatible silico-tungsten oxide shell. The particles can be functionalized, optically detected, and optically manipulated. To show the functionalization the fluorescent dye NOPS was bound to the FePt core-shell nanoparticles with propyl-triethoxy-silane linkers and fluorescence of the labeled particles were observed in ethanol (EtOH). In aqueous dispersion the NOPS fluorescence is quenched making them invisible using 1-photon excitation. However, we observe bright luminescence of labeled and even unlabeled magnetic core-shell nanoparticles with multi-photon excitation. Luminescence can be detected in the near ultraviolet and the full visible spectral range by near infrared multi-photon excitation. For optical manipulation, we were able to drag clusters of particles, and maybe also single particles, by a focused laser beam that acts as optical tweezers by inducing an electric dipole in the insulated metal nanoparticles. In a first application, we show that the luminescence of the core-shell nanoparticles is bright enough for in vivo multi-photon imaging in the mouse neocortex down to cortical layer 5.
Optical absorption of carbon-gold core-shell nanoparticles
NASA Astrophysics Data System (ADS)
Wang, Zhaolong; Quan, Xiaojun; Zhang, Zhuomin; Cheng, Ping
2018-01-01
In order to enhance the solar thermal energy conversion efficiency, we propose to use carbon-gold core-shell nanoparticles dispersed in liquid water. This work demonstrates theoretically that an absorbing carbon (C) core enclosed in a plasmonic gold (Au) nanoshell can enhance the absorption peak while broadening the absorption band; giving rise to a much higher solar absorption than most previously studied core-shell combinations. The exact Mie solution is used to evaluate the absorption efficiency factor of spherical nanoparticles in the wavelength region from 300 nm to 1100 nm as well as the electric field and power dissipation profiles inside the nanoparticles at specified wavelengths (mostly at the localized surface plasmon resonance wavelength). The field enhancement by the localized plasmons at the gold surfaces boosts the absorption of the carbon particle, resulting in a redshift of the absorption peak with increased peak height and bandwidth. In addition to spherical nanoparticles, we use the finite-difference time-domain method to calculate the absorption of cubic core-shell nanoparticles. Even stronger enhancement can be achieved with cubic C-Au core-shell structures due to the localized plasmonic resonances at the sharp edges of the Au shell. The solar absorption efficiency factor can exceed 1.5 in the spherical case and reach 2.3 in the cubic case with a shell thickness of 10 nm. Such broadband absorption enhancement is in great demand for solar thermal applications including steam generation.
Joshi, Deepika P; Pant, Geeta; Arora, Neha; Nainwal, Seema
2017-02-01
Present work describes the formation of α-Fe 2 O 3 @SiO 2 core shell structure by systematic layer by layer deposition of silica shell on core iron oxide nanoparticles prepared via various solvents. Sol-gel method has been used to synthesize magnetic core and the dielectric shell. The average crystallite size of iron oxide nanoparticles was calculated ∼20 nm by X-ray diffraction pattern. Morphological study by scanning electron microscopy revealed that the core-shell nanoparticles were spherical in shape and the average size of nanoparticles increased by varying solvent from methanol to ethanol to isopropanol due to different chemical structure and nature of the solvents. It was also observed that the particles prepared by solvent ethanol were more regular and homogeneous as compared to other solvents. Magnetic measurements showed the weak ferromagnetic behaviour of both core α-Fe 2 O 3 and silica-coated iron oxide nanoparticles which remained same irrespective of the solvent chosen. However, magnetization showed dependency on the types of solvent chosen due to the variation in shell thickness. At room temperature, dielectric constant and dielectric loss of silica nanoparticles for all the solvents showed decrement with the increment in frequency. Decrement in the value of dielectric constant and increment in dielectric loss was observed for silica coated iron oxide nanoparticles in comparison of pure silica, due to the presence of metallic core. Homogeneous and regular silica layer prepared by using ethanol as a solvent could serve as protecting layer to shield the magnetic behaviour of iron oxide nanoparticles as well as to provide better thermal insulation over pure α-Fe 2 O 3 nanoparticles.
NASA Astrophysics Data System (ADS)
Heidarzadeh, Hamid
2018-03-01
Significant performance enhancement in an ultrathin perovskite (CH3NH3PbI3) solar cell is done using plasmonic embedded core–shell dimer nanoparticles. Three-dimensional finite difference time-domain (FDTD) method is used. A perovskite absorber with a volume of 400 × 400 × 200 nm3 is considered. At first, a cell with one embedded nanoparticle is simulated. Absorptance of CH3NH3PbI3 absorber and gold nanoparticle are obtained. An optimization is done. Then a cell with embedded dimer nanoparticles is evaluated. The results show higher photocurrent enhancement for that in compared to a cell with one embedded nanoparticle. To further photocurrent enhancement, gold-SiO2 core–shell nanoparticles are used. Photocurrents of 23.37 mA cm‑2, 23.3 mA cm‑2, 22.5 mA cm‑2 and 21.47 mA cm‑2 are obtained for a cell with two embedded core–shell nanoparticles with core radius of 60 nm and shell thickness of 2 nm, 5 nm, 10 nm and 20 nm, respectively. It is important to mention that the photocurrent is 17.9 mA cm‑2 for reference cell and 19.8 mA cm‑2 for a cell with one embedded nanoparticle. Higher photocurrent is due to the near-field plasmonic effect.
Green synthesis and characterization of size tunable silica-capped gold core-shell nanoparticles
NASA Astrophysics Data System (ADS)
Wangoo, Nishima; Shekhawat, Gajendra; Wu, Jin-Song; Bhasin, Aman K. K.; Suri, C. R.; Bhasin, K. K.; Dravid, Vinayak
2012-08-01
Silica-coated gold nanoparticles (Au@SiO2) with controlled silica-shell thickness were prepared by a modified Stober's method using 10-nm gold nanoparticles (AuNPs) as seeds. The AuNPs were silica-coated with a sol-gel reaction using tetraethylorthosilicate (TEOS) as a silica source and ammonia as a catalyst. An increase in TEOS concentration resulted in an increase in shell thickness. The NPs were characterized by transmission electron microscopy, selected area electron diffraction, energy-dispersive X-ray spectroscopy, scanning near-field ultrasound holography and scanning transmission electron microscopy. The method required no surface modification and the synthesized core shell nanoparticles can be used for various types of biological applications.
Modified ferrite core-shell nanoparticles magneto-structural characterization
NASA Astrophysics Data System (ADS)
Klekotka, Urszula; Piotrowska, Beata; Satuła, Dariusz; Kalska-Szostko, Beata
2018-06-01
In this study, ferrite nanoparticles with core-shell structures and different chemical compositions of both the core and shell were prepared with success. Proposed nanoparticles have in the first and second series magnetite core, and the shell is composed of a mixture of ferrites with Fe3+, Fe2+ and M ions (where M = Co2+, Mn2+ or Ni2+) with a general composition of M0.5Fe2.5O4. In the third series, the composition is inverted, the core is composed of a mixture of ferrites and as a shell magnetite is placed. Morphology and structural characterization of nanoparticles were done using Transmission Electron Microscopy (TEM), X-ray diffraction (XRD), and Infrared spectroscopy (IR). While room temperature magnetic properties were measured using Mössbauer spectroscopy (MS). It is seen from Mössbauer measurements that Co always increases hyperfine magnetic field on Fe atoms at RT, while Ni and Mn have opposite influences in comparison to pure Fe ferrite, regardless of the nanoparticles structure.
Allen, Brett L; Johnson, Jermaine D; Walker, Jeremy P
2012-07-27
In the advancement of green syntheses and sustainable reactions, enzymatic biocatalysis offers extremely high reaction rates and selectivity that goes far beyond the reach of chemical catalysts; however, these enzymes suffer from typical environmental constraints, e.g. operational temperature, pH and tolerance to oxidative environments. A common hydrolase enzyme, diisopropylfluorophosphatase (DFPase, EC 3.1.8.2), has demonstrated a pronounced efficacy for the hydrolysis of a variety of substrates for potential toxin remediation, but suffers from the aforementioned limitations. As a means to enhance DFPase's stability in oxidative environments, enzymatic covalent immobilization within the polymeric matrix of poly(propylene sulfide) (PPS) nanoparticles was performed. By modifying the enzyme's exposed lysine residues via thiolation, DFPase is utilized as a comonomer/crosslinker in a mild emulsion polymerization. The resultant polymeric polysulfide shell acts as a 'sacrificial barrier' by first oxidizing to polysulfoxides and polysulfones, rendering DFPase in an active state. DFPase-PPS nanoparticles thus retain activity upon exposure to as high as 50 parts per million (ppm) of hypochlorous acid (HOCl), while native DFPase is observed as inactive at 500 parts per billion (ppb). This trend is also confirmed by enzyme-generated (chloroperoxidase (CPO), EC 1.11.1.10) reactive oxygen species (ROS) including both HOCl (3 ppm) and ClO(2) (100 ppm).
Ma, Jiachen; Zhang, Luqing; Geng, Bing; Azhar, Umair; Xu, Anhou; Zhang, Shuxiang
2017-01-25
In this work, a thermo-responsive and cross-linked fluoropolymer poly(2,2,2-Trifluoroethyl) methacrylate (PTFEMA) was successfully prepared by reversible addition-fragmentation chain transfer (RAFT) mediated aqueous polymerization with a thermo-responsive diblock poly(dimethylacrylamide- b - N -isopropylacrylamide) (PDMA- b -PNIPAM) that performed a dual function as both a nanoreactor and macro-RAFT agent. The cross-linked polymer particles proved to be in a spherical-like structure of about 50 nm in diameter and with a relatively narrow particle size distribution. ¹H-NMR and 19 F-NMR spectra showed that thermo-responsive diblock P(DMA- b -NIPAM) and cross-linked PTFEMA particles were successfully synthesized. Influence of the amount of ammonium persulfate (APS), the molar ratio of monomers to RAFT agent, influence of the amount of cross-linker on aqueous polymerization and thermo-responsive characterization of the particles are investigated. Monomer conversion increased from 44% to 94% with increasing the molar ratio of APS and P(DMA- b -NIPAM) from 1:9 to1:3. As the reaction proceeded, the particle size increased from 29 to 49 nm due to the consumption of TFEMA monomer. The size of cross-linked nanoparticles sharply decreased from 50.3 to 40.5 nm over the temperature range 14-44 °C, suggesting good temperature sensitivity for these nanoparticles.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gunawidjaja, Ray; Diez-y-Riega, Helena; Eilers, Hergen, E-mail: eilers@wsu.edu
2015-09-15
Amorphous precursors of Eu-doped-ZrO{sub 2}/Tb-doped-Y{sub 2}O{sub 3} (p-Eu:ZrO{sub 2}/p-Tb:Y{sub 2}O{sub 3}) core/shell nanoparticles are rapidly heated to temperatures between 200 °C and 950 °C for periods between 2 s and 60 s using a CO{sub 2} laser. During this heating process the nanoparticles undergo irreversible phase changes. The fluorescence spectra due to Eu{sup 3+} dopants in the core and Tb{sup 3+} dopants in the shell are used to identify distinct phases within the material and to generate time/temperature phase diagrams. Such phase diagrams can potentially help to determine unknown time/temperature histories in thermosensor applications. - Graphical abstract: A CO{sub 2}more » laser is used for rapid heating of p-Eu:ZrO{sub 2}/p-Tb:Y{sub 2}O{sub 3} core/shell nanoparticles. Optical spectra are used to identify distinct phases and to determine its thermal history. - Highlights: • Synthesized oxide precursors of lanthanide doped core/shell nanoparticles. • Heated core/shell nanoparticles via laser-based T-jump technique. • Observed time- and temperature-dependent irreversible phase transition.« less
Beck, Emily C.; Lohman, Brooke L.; Tabakh, Daniel B.; Kieweg, Sarah L.; Gehrke, Stevin H.; Berkland, Cory J.; Detamore, Michael S.
2015-01-01
Hydrogels are a promising class of materials for tissue regeneration, but they lack the ability to be molded into a defect site by a surgeon because hydrogel precursors are liquid solutions that are prone to leaking during placement. Therefore, although the main focus of hydrogel technology and developments are on hydrogels in their crosslinked form, our primary focus is on improving the fluid behavior of hydrogel precursor solutions. In this work, we introduce a method to achieve paste-like hydrogel precursor solutions by combining hyaluronic acid nanoparticles with traditional crosslinked hyaluronic acid hydrogels. Prior to crosslinking, the samples underwent rheological testing to assess yield stress and recovery using linear hyaluronic acid as a control. The experimental groups containing nanoparticles were the only solutions that exhibited a yield stress, demonstrating that the nanoparticulate rather than the linear form of hyaluronic acid was necessary to achieve paste-like behavior. The gels were also photocrosslinked and further characterized as solids, where it was demonstrated that the inclusion of nanoparticles did not adversely affect the compressive modulus and that encapsulated bone marrow-derived mesenchymal stem cells remained viable. Overall, this nanoparticle-based approach provides a platform hydrogel system that exhibits a yield stress prior to crosslinking, and can then be crosslinked into a hydrogel that is capable of encapsulating cells that remain viable. This behavior may hold significant impact for hydrogel applications where a paste-like behavior is desired in the hydrogel precursor solution. PMID:25691398
Li, Zheng; Gu, Liwei
2014-02-12
Nanoparticles have the potential to increase bioavailability of nutraceutical compounds such as (-)-epigallocatechin gallate (EGCG). Ovalbumin was conjugated with dextran using the Maillard reaction. The resultant ovalbumin-dextran (O-D) conjugates were self-assembled with EGCG to form EGCG O-D conjugate nanoparticles at pH 5.2 after heating at 80 °C for 60 min. Ovalbumin in EGCG O-D conjugate nanoparticles was further cross-linked by glutaraldehyde for 24 h at room temperature. EGCG O-D conjugate nanoparticles and cross-linked EGCG O-D conjugate nanoparticles in aqueous suspension had particle sizes of 285 and 339 nm, respectively, and showed a spherical morphology. The loading efficiencies of EGCG in these two nanoparticles were 23.4 and 30.0%, whereas the loading capacities were 19.6 and 20.9%, respectively. These nanoparticles showed positive zeta-potentials in a pH range from 2.5 to 4.0 but had negative charges at pH ≥5.0. EGCG O-D conjugate nanoparticles maintained a particle size of 183-349 nm in simulated gastric fluid (SGF) and 188-291 nm in simulated intestinal fluid (SIF) at 37 °C for 2 h, whereas cross-linked nanoparticles had particle sizes of 294-527 nm in SGF and 206-300 nm in SIF. Limited release of EGCG was observed in both nanoparticle systems in simulated gastric and intestinal fluids without and with digestive enzymes. EGCG O-D conjugate nanoparticles significantly enhanced the apparent permeability coefficient (Papp) of EGCG on Caco-2 monolayers compared with EGCG solution, suggesting that these nanoparticles may improve the absorption of EGCG.
NASA Astrophysics Data System (ADS)
Chen, Rui; Zhang, Jinfeng; Wang, Yu; Chen, Xianfeng; Zapien, J. Antonio; Lee, Chun-Sing
2015-10-01
Recently, nanoscale metal-organic frameworks (NMOFs) have started to be developed as a promising platform for bioimaging and drug delivery. On the other hand, combination therapies using multiple approaches are demonstrated to achieve much enhanced efficacy. Herein, we report, for the first time, core-shell nanoparticles consisting of a photodynamic therapeutic (PDT) agent and a MOF shell while simultaneously carrying a chemotherapeutic drug for effective combination therapy. In this work, core-shell nanoparticles of zeolitic-imadazolate framework-8 (ZIF-8) as shell embedded with graphitic carbon nitride (g-C3N4) nanosheets as core are fabricated by growing ZIF-8 in the presence of g-C3N4 nanosheets. Doxorubicin hydrochloride (DOX) is then loaded into the ZIF-8 shell of the core-shell nanoparticles. The combination of the chemotherapeutic effects of DOX and the PDT effect of g-C3N4 nanosheets can lead to considerably enhanced efficacy. Furthermore, the red fluorescence of DOX and the blue fluorescence of g-C3N4 nanosheets provide the additional function of dual-color imaging for monitoring the drug release process.Recently, nanoscale metal-organic frameworks (NMOFs) have started to be developed as a promising platform for bioimaging and drug delivery. On the other hand, combination therapies using multiple approaches are demonstrated to achieve much enhanced efficacy. Herein, we report, for the first time, core-shell nanoparticles consisting of a photodynamic therapeutic (PDT) agent and a MOF shell while simultaneously carrying a chemotherapeutic drug for effective combination therapy. In this work, core-shell nanoparticles of zeolitic-imadazolate framework-8 (ZIF-8) as shell embedded with graphitic carbon nitride (g-C3N4) nanosheets as core are fabricated by growing ZIF-8 in the presence of g-C3N4 nanosheets. Doxorubicin hydrochloride (DOX) is then loaded into the ZIF-8 shell of the core-shell nanoparticles. The combination of the chemotherapeutic effects of DOX and the PDT effect of g-C3N4 nanosheets can lead to considerably enhanced efficacy. Furthermore, the red fluorescence of DOX and the blue fluorescence of g-C3N4 nanosheets provide the additional function of dual-color imaging for monitoring the drug release process. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr04436g
NASA Astrophysics Data System (ADS)
Chen, Jian; Zeng, Fang; Wu, Shuizhu; Su, Junhua; Zhao, Jianqing; Tong, Zhen
2009-09-01
A facile approach was developed to produce a dye-doped core-shell nanoparticle chemosensor for detecting Cu2+ in aqueous media. The core-shell nanoparticle sensor was prepared by a one-step emulsifier-free polymerization, followed by the doping of the fluorescent dye Nile red (9-diethylamino- 5H-benzo[alpha] phenoxazine-5-one, NR) into the particles. For the nanoparticles, the hydrophilic polyethyleneimine (PEI) chain segments serve as the shell and the hydrophobic polymethyl methacrylate (PMMA) constitutes the core of the nanoparticles. The non-toxic and biocompatible PEI chain segments on the nanoparticle surface exhibit a high affinity for Cu2+ ions in aqueous media, and the quenching of the NR fluorescence is observed upon binding of Cu2+ ions. This makes the core-shell nanoparticle system a water-dispersible chemosensor for Cu2+ ion detection. The quenching of fluorescence arises through intraparticle energy transfer (FRET) from the dye in the hydrophobic PMMA core to the Cu2+/PEI complexes on the nanoparticle surface. The energy transfer efficiency for PEI/PMMA particles with different diameters was determined, and it is found that the smaller nanoparticle sample exhibits higher quenching efficiency, and the limit for Cu2+ detection is 1 µM for a nanoparticle sample with a diameter of ~30 nm. The response of the fluorescent nanoparticle towards different metal ions was investigated and the nanoparticle chemosensor displays high selectivity and antidisturbance for the Cu2+ ion among the metal ions examined (Na+, K+, Mg2+, Ca2+, Zn2+, Hg2+, Mn2+, Fe2+, Ni2+, Co2+ and Pb2+). This emulsifier-free, biocompatible and sensitive fluorescent nanoparticle sensor may find applications in cupric ion detection in the biological and environmental areas.
Chen, Jian; Zeng, Fang; Wu, Shuizhu; Su, Junhua; Zhao, Jianqing; Tong, Zhen
2009-09-09
A facile approach was developed to produce a dye-doped core-shell nanoparticle chemosensor for detecting Cu(2+) in aqueous media. The core-shell nanoparticle sensor was prepared by a one-step emulsifier-free polymerization, followed by the doping of the fluorescent dye Nile red (9-diethylamino- 5H-benzo[alpha] phenoxazine-5-one, NR) into the particles. For the nanoparticles, the hydrophilic polyethyleneimine (PEI) chain segments serve as the shell and the hydrophobic polymethyl methacrylate (PMMA) constitutes the core of the nanoparticles. The non-toxic and biocompatible PEI chain segments on the nanoparticle surface exhibit a high affinity for Cu(2+) ions in aqueous media, and the quenching of the NR fluorescence is observed upon binding of Cu(2+) ions. This makes the core-shell nanoparticle system a water-dispersible chemosensor for Cu(2+) ion detection. The quenching of fluorescence arises through intraparticle energy transfer (FRET) from the dye in the hydrophobic PMMA core to the Cu(2+)/PEI complexes on the nanoparticle surface. The energy transfer efficiency for PEI/PMMA particles with different diameters was determined, and it is found that the smaller nanoparticle sample exhibits higher quenching efficiency, and the limit for Cu(2+) detection is 1 microM for a nanoparticle sample with a diameter of approximately 30 nm. The response of the fluorescent nanoparticle towards different metal ions was investigated and the nanoparticle chemosensor displays high selectivity and antidisturbance for the Cu(2+) ion among the metal ions examined (Na(+), K(+), Mg(2+), Ca(2+), Zn(2+), Hg(2+), Mn(2+), Fe(2+), Ni(2+), Co(2+) and Pb(2+)). This emulsifier-free, biocompatible and sensitive fluorescent nanoparticle sensor may find applications in cupric ion detection in the biological and environmental areas.
Sulfur containing nanoporous materials, nanoparticles, methods and applications
Archer, Lynden A.; Navaneedhakrishnan, Jayaprakash
2018-01-30
Sulfur containing nanoparticles that may be used within cathode electrodes within lithium ion batteries include in a first instance porous carbon shape materials (i.e., either nanoparticle shapes or "bulk" shapes that are subsequently ground to nanoparticle shapes) that are infused with a sulfur material. A synthetic route to these carbon and sulfur containing nanoparticles may use a template nanoparticle to form a hollow carbon shape shell, and subsequent dissolution of the template nanoparticle prior to infusion of the hollow carbon shape shell with a sulfur material. Sulfur infusion into other porous carbon shapes that are not hollow is also contemplated. A second type of sulfur containing nanoparticle includes a metal oxide material core upon which is located a shell layer that includes a vulcanized polymultiene polymer material and ion conducting polymer material. The foregoing sulfur containing nanoparticle materials provide the electrodes and lithium ion batteries with enhanced performance.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kang, Jie; Li, Yuan; Chen, Yingnan
Highlights: • Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses were prepared via the Stöber process. • Sm and Dy complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. • The complex-doped Ag@SiO{sub 2} composites show stronger luminescent intensities than pure complexes. • The luminescent intensities of the composites strongly depend on the SiO{sub 2} shell thickness. - Abstract: Three kinds of almost spherical core–shell Ag@SiO{sub 2} nanoparticles of different silica shell thicknesses (10, 25 and 80 nm) were prepared via the Stöber process. The Ag core nanoparticles were prepared by reducing silver nitrate with sodium citrate. The size, morphology andmore » structure of core–shell Ag@SiO{sub 2} nanoparticles were characterized by transmission electron microscopy. Subsequently, eight kinds of lanthanide complexes with benzoate, 1,10-phenanthroline and 2,2′-bipyridine were synthesized. The composition of the lanthanide complexes was characterized by elemental analysis, IR and UV spectra. Finally, lanthanide complexes were attached to the surface of Ag@SiO{sub 2} nanoparticles to form lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites. The results show that the complex-doped Ag@SiO{sub 2} nanocomposites display much stronger luminescence intensities than the lanthanide complexes. Furthermore, the luminescence intensities of the lanthanide-complex-doped Ag@SiO{sub 2} nanocomposites with SiO{sub 2} shell thickness of 25 nm are stronger than those of the nanocomposites with SiO{sub 2} shell thickness of 10 and 80 nm.« less
Predicted trends of core-shell preferences for 132 late transition-metal binary-alloy nanoparticles.
Wang, Lin-Lin; Johnson, Duane D
2009-10-07
Transition-metal alloyed nanoparticles with core-shell features (shell enrichment by one of the metals) are becoming ubiquitous, from (electro-)catalysis to biomedical applications, due to their size control, performance, biocompatibility, and cost. We investigate 132 binary-alloyed nanoparticle systems (groups 8 to 11 in the Periodic Table) using density functional theory (DFT) and systematically explore their segregation energies to determine core-shell preferences. We find that core-shell preferences are generally described by two independent factors: (1) cohesive energy (related to vapor pressure) and (2) atomic size (quantified by the Wigner-Seitz radius), and the interplay between them. These independent factors are shown to provide general trends for the surface segregation preference for atoms in nanoparticles, as well as semi-infinite surfaces, and give a simple correlation (a "design map") for the alloying and catalytic behavior. Finally, we provide a universal description of core-shell preference via tight-binding theory (band-energy differences) that (i) quantitatively reproduces the DFT segregation energies and (ii) confirms the electronic origins and correlations for core-shell behavior.
Rahman, Md Mahbubor; Chehimi, Mohamed M; Fessi, Hatem; Elaissari, Abdelhamid
2011-08-15
Temperature responsive magnetic polymer submicron particles were prepared by two step seed emulsion polymerization process. First, magnetic seed polymer particles were obtained by emulsion polymerization of styrene using potassium persulfate (KPS) as an initiator and divinylbenzne (DVB) as a cross-linker in the presence of oil-in-water magnetic emulsion (organic ferrofluid droplets). Thereafter, DVB cross-linked magnetic polymer particles were used as seed in the precipitation polymerization of N-isopropylacrylamide (NIPAM) to induce thermosensitive PNIPAM shell onto the hydrophobic polymer surface of the cross-linked magnetic polymer particles. To impart cationic functional groups in the thermosensitive PNIPAM backbone, the functional monomer aminoethylmethacrylate hydrochloride (AEMH) was used to polymerize with NIPAM while N,N'-methylenebisacrylamide (MBA) and 2, 2'-azobis (2-methylpropionamidine) dihydrochloride (V-50) were used as a cross-linker and as an initiator respectively. The effect of seed to monomer (w/w) ratio along with seed nature on the final particle morphology was investigated. Dynamic light scattering (DLS) results demonstrated particles swelling at below volume phase transition temperature (VPTT) and deswelling above the VPTT. The perfect core (magnetic) shell (polymer) structure of the particles prepared was confirmed by Transmission Electron Microscopy (TEM). The chemical composition of the particles were determined by thermogravimetric analysis (TGA). The effect of temperature, pH, ionic strength on the colloidal properties such as size and zeta potential of the micron sized thermo-sensitive magnetic particles were also studied. In addition, a short mechanistic discussion on the formation of core-shell morphology of magnetic polymer particles has also been discussed. Copyright © 2011 Elsevier Inc. All rights reserved.
NASA Astrophysics Data System (ADS)
Benedetti, Cesare; Flouda, Paraskevi; Antonello, Alice; Rosenauer, Christine; Pérez-Pla, Francisco F.; Landfester, Katharina; Gross, Silvia; Muñoz-Espí, Rafael
2017-09-01
The photoactivated free radical miniemulsion copolymerization of methyl methacrylate (MMA) and the zirconium oxocluster Zr4O2(methacrylate)12 is used as an effective and fast preparation method for polymer/inorganic hybrid nanoparticles. The oxoclusters, covalently anchored to the polymer network, act as metal-organic cross-linkers, thus improving the thermomechanical properties of the resulting hybrid nanoparticles. Benzoin carbonyl organic compounds were used as photoinitiators. The obtained materials are compared in terms of cross-linking, effectiveness of cluster incorporation, and size distribution with the analogous nanoparticles produced by using conventional thermally induced free radical miniemulsion copolymerization. The kinetics of the polymerization process in the absence and in the presence of the oxocluster is also investigated.
Peng, Bei; Locascio, Mark; Zapol, Peter; Li, Shuyou; Mielke, Steven L; Schatz, George C; Espinosa, Horacio D
2008-10-01
The excellent mechanical properties of carbon nanotubes are being exploited in a growing number of applications from ballistic armour to nanoelectronics. However, measurements of these properties have not achieved the values predicted by theory due to a combination of artifacts introduced during sample preparation and inadequate measurements. Here we report multiwalled carbon nanotubes with a mean fracture strength >100 GPa, which exceeds earlier observations by a factor of approximately three. These results are in excellent agreement with quantum-mechanical estimates for nanotubes containing only an occasional vacancy defect, and are approximately 80% of the values expected for defect-free tubes. This performance is made possible by omitting chemical treatments from the sample preparation process, thus avoiding the formation of defects. High-resolution imaging was used to directly determine the number of fractured shells and the chirality of the outer shell. Electron irradiation at 200 keV for 10, 100 and 1,800 s led to improvements in the maximum sustainable loads by factors of 2.4, 7.9 and 11.6 compared with non-irradiated samples of similar diameter. This effect is attributed to crosslinking between the shells. Computer simulations also illustrate the effects of various irradiation-induced crosslinking defects on load sharing between the shells.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Peng, B.; Locascio, M.; Zapol, P.
2008-01-01
The excellent mechanical properties of carbon nanotubes are being exploited in a growing number of applications from ballistic armour to nanoelectronics. However, measurements of these properties have not achieved the values predicted by theory due to a combination of artifacts introduced during sample preparation and inadequate measurements. Here we report multiwalled carbon nanotubes with a mean fracture strength >100 GPa, which exceeds earlier observations by a factor of approximately three. These results are in excellent agreement with quantum-mechanical estimates for nanotubes containing only an occasional vacancy defect, and are {approx}80% of the values expected for defect-free tubes. This performance ismore » made possible by omitting chemical treatments from the sample preparation process, thus avoiding the formation of defects. High-resolution imaging was used to directly determine the number of fractured shells and the chirality of the outer shell. Electron irradiation at 200 keV for 10, 100 and 1,800 s led to improvements in the maximum sustainable loads by factors of 2.4, 7.9 and 11.6 compared with non-irradiated samples of similar diameter. This effect is attributed to crosslinking between the shells. Computer simulations also illustrate the effects of various irradiation-induced crosslinking defects on load sharing between the shells.« less
Non-aqueous synthesis of water-dispersible Fe3O4-Ca3(PO4)2 core-shell nanoparticles
NASA Astrophysics Data System (ADS)
Liu, HongLing; Wu, JunHua; Min, Ji Hyun; Hou, Peng; Song, Ah-Young; Kim, Young Keun
2011-02-01
The Fe3O4-Ca3(PO4)2 core-shell nanoparticles were prepared by one-pot non-aqueous nanoemulsion with the assistance of a biocompatible triblock copolymer, poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO), integrating the magnetic properties of Fe3O4 and the bioactive functions of Ca3(PO4)2 into single entities. The Fe3O4 nanoparticles were pre-formed first by thermal reduction of Fe(acac)3 and then the Ca3(PO4)2 layer was coated by simultaneous deposition of Ca2 + and PO43 - . The characterization shows that the combination of the two materials into a core-shell nanostructure retains the magnetic properties and the Ca3(PO4)2 shell forms an hcp phase (a = 7.490 Å, c = 9.534 Å) on the Fe3O4 surface. The magnetic hysteresis curves of the nanoparticles were further elucidated by the Langevin equation, giving an estimation of the effective magnetic dimension of the nanoparticles and reflecting the enhanced susceptibility response as a result of the surface covering. Fourier transform infrared (FTIR) analysis provides the characteristic vibrations of Ca3(PO4)2 and the presence of the polymer surfactant on the nanoparticle surface. Moreover, the nanoparticles could be directly transferred to water and the aqueous dispersion-collection process of the nanoparticles was demonstrated for application readiness of such core-shell nanostructures in an aqueous medium. Thus, the construction of Fe3O4 and Ca3(PO4)2 in the core-shell nanostructure has conspicuously led to enhanced performance and multi-functionalities, offering various possible applications of the nanoparticles.
Huang, Shuangshuang; Yang, Nating; Wang, Shibin; Sun, Yuhan; Zhu, Yan
2016-08-07
Pt-Cu nanoparticles constructed with a hollow core and porous shell have been synthesized in which Pt-Cu cages with multiporous outermost shells are formed at the initial stage and then the Pt and Cu atoms in solution continuously fed these hollow-core of cages by passing through the porous tunnels of the outermost shells, finally leading to the formation of hollow structures with different sizes. Furthermore, these hollow-core Pt-Cu nanoparticles are more effective than the solid-core Pt-Cu nanoparticles for the catalytic hydrogenation of furfural toward furfuryl alcohol. The former can achieve almost 100% conversion of furfural with 100% selectivity toward the alcohol.
NASA Astrophysics Data System (ADS)
Roberts, Stephen K.
Nanomaterials show immense promise for the future in numerous areas of application. Properties that are unique from the bulk material and are tunable allow for innovation in material design. This thesis will focus on controlling the physical properties of core/shell nanostructures to enhance the utility of the materials. The first focus is on the impact of different solvent mixtures during the shell growth phase of SILAR based core/shell quantum dot synthesis is studied. Gaining insight into the mechanism for SILAR growth of core/shell nanoparticles allows improved synthetic yields and precursor binding, providing enhanced control to synthesis of core/shell nanoparticles. The second focus of this thesis is exploring the use of magnetic nanoparticles for magnetic drug targeting for cardiovascular conditions. Magnetic targeting for drug delivery enables increased local drug concentration, while minimizing non-specific interactions. In order to be effective for magnetic targeting, it must be shown that low magnetic strength is sufficient to capture flowing nanoparticles. By demonstrating the binding of a therapeutic agent to the surface at medicinal levels, the viability for use as a nanoparticle drug delivery system is improved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Desautels, R. D., E-mail: rddesautels@physics.umanitoba.ca; Toyota Research Institute of North America, Ann Arbor, Michigan 48169; Freeland, J. W.
2015-05-07
We have investigated the role of spontaneously formed interfacial metal silicates on the magnetism of FeCo/SiO{sub 2} and Fe{sub 49%}Co{sub 49%}V{sub 2%}/SiO{sub 2} core/shell nanoparticles. Element specific x-ray absorption and photoelectron spectroscopy experiments have identified the characteristic spectral features of metallic iron and cobalt from within the nanoparticle core. In addition, metal silicates of iron, cobalt, and vanadium were found to have formed spontaneously at the interface between the nanoparticle core and silica shell. X-ray magnetic circular dichroism experiments indicated that the elemental magnetism was a result of metallic iron and cobalt with small components from the iron, cobalt, andmore » vanadium silicates. Magnetometry experiments have shown that there was no exchange bias loop shift in the FeCo nanoparticles; however, exchange bias from antiferromagnetic vanadium oxide was measured in the V-doped nanoparticles. These results showed clearly that the interfacial metal silicates played a significant role in the magnetism of these core/shell nanoparticles, and that the vanadium percolated from the FeCo-cores into the SiO{sub 2}-based interfacial shell.« less
Electronically cloaked nanoparticles
NASA Astrophysics Data System (ADS)
Shen, Wenqing
The concept of electronic cloaking is to design objects invisible to conduction electrons. The approach of electronic cloaking has been recently suggested to design invisible nanoparticle dopants with electronic scattering cross section smaller than 1% of the physical cross section (pi a2), and therefore to enhance the carrier mobility of bulk materials. The proposed nanoparticles have core-shell structures. The dopants are incorporated inside the core, while the shell layer serves both as a spacer to separate the charge carriers from their parent atoms and as a cloaking shell to minimize the scattering cross section of the electrons from the ionized nanoparticles. Thermoelectric materials are usually highly doped to have enough carrier density. Using invisible dopants could achieve larger thermoelectric power factors by enhancing the electronic mobility. Core-shell nanoparticles show an advantage over one-layer nanoparticles, which are proposed in three-dimensional modulation doping. However designing such nanoparticles is not easy as there are too many parameters to be considered. This thesis first shows an approach to design hollow nanoparticles by applying constrains on variables. In the second part, a simple mapping approach is introduced where one can identify possible core-shell particles by comparing the dimensionless parameters of chosen materials with provided maps. In both parts of this work, several designs with realistic materials were made and proven to achieve electronic cloaking. Improvement in the thermoelectric power factor compared to the traditional impurity doping method was demonstrated in several cases.
Scalable Super-Resolution Synthesis of Core-Vest Composites Assisted by Surface Plasmons.
Montazeri, A O; Kim, Y; Fang, Y S; Soheilinia, N; Zaghi, G; Clark, J K; Maboudian, R; Kherani, N P; Carraro, C
2018-02-15
The behavior of composite nanostructures depends on both size and elemental composition. Accordingly, concurrent control of size, shape, and composition of nanoparticles is key to tuning their functionality. In typical core-shell nanoparticles, the high degree of symmetry during shell formation results in fully encapsulated cores with severed access to the surroundings. We commingle light parameters (wavelength, intensity, and pulse duration) with the physical properties of nanoparticles (size, shape, and composition) to form hitherto unrealized core-vest composite nanostructures (CVNs). Unlike typical core-shells, the plasmonic core of the resulting CVNs selectively maintains physical access to its surrounding. Tunable variations in local temperature profiles ≳50 °C are plasmonically induced over starburst-shaped nanoparticles as small as 50-100 nm. These temperature variations result in CVNs where the shell coverage mirrors the temperature variations. The precision thus offered individually tailors access pathways of the core and the shell.
Chung, Ren-Jei; Shih, Hui-Ting
2014-01-24
Iron core gold shell nanoparticles grafted with Methotrexate (MTX) and indocyanine green (ICG) were synthesized for the first time in this study, and preliminarily evaluated for their potential in magnetic hyperthermia treatment. The core-shell Fe@Au nanoparticles were prepared via the microemulsion process and then grafted with MTX and ICG using hydrolyzed poly(styrene-alt-maleic acid) (PSMA) to obtain core-shell Fe@Au-PSMA-ICG/MTX nanoparticles. MTX is an anti-cancer therapeutic, and ICG is a fluorescent dye. XRD, TEM, FTIR and UV-Vis spectrometry were performed to characterize the nanoparticles. The data indicated that the average size of the nanoparticles was 6.4 ± 09 nm and that the Au coating protected the Fe core from oxidation. MTX and ICG were successfully grafted onto the surface of the nanoparticles. Under exposure to high frequency induction waves, the superparamagnetic nanoparticles elevated the temperature of a solution in a few minutes, which suggested the potential for an application in magnetic hyperthermia treatment. The in vitro studies verified that the nanoparticles were biocompatible; nonetheless, the Fe@Au-PSMA-ICG/MTX nanoparticles killed cancer cells (Hep-G2) via the magnetic hyperthermia mechanism and the release of MTX.
Determining the size of nanoparticles in the example of magnetic iron oxide core-shell systems
NASA Astrophysics Data System (ADS)
Jarzębski, Maciej; Kościński, Mikołaj; Białopiotrowicz, Tomasz
2017-08-01
The size of nanoparticles is one of the most important factors for their possible applications. Various techniques for the nanoparticle size characterization are available. In this paper selected techniques will be considered base on the prepared core-shell magnetite nanoparticles. Magnetite is one of the most investigated and developed magnetic material. It shows interesting magnetic properties which can be used for biomedical applications, such as drug delivery, hypothermia and also as a contrast agent. To reduce the toxic effects of Fe3O4, magnetic core was covered by dextran and gelatin. Moreover, the shell was doped by fluorescent dye for confocal microscopy investigation. The main investigation focused on the methods for particles size determination of modified magnetite nanoparticles prepared with different techniques. The size distribution were obtained by nanoparticle tracking analysis, dynamic light scattering and transmission electron microscopy. Furthermore, fluorescent correlation spectroscopy (FCS) and confocal microscopy were used to compare the results for particle size determination of core-shell systems.
Core-Shell Magnetic Morphology of Structurally Uniform Magnetite Nanoparticles
NASA Astrophysics Data System (ADS)
Krycka, K. L.; Booth, R. A.; Hogg, C. R.; Ijiri, Y.; Borchers, J. A.; Chen, W. C.; Watson, S. M.; Laver, M.; Gentile, T. R.; Dedon, L. R.; Harris, S.; Rhyne, J. J.; Majetich, S. A.
2010-05-01
A new development in small-angle neutron scattering with polarization analysis allows us to directly extract the average spatial distributions of magnetic moments and their correlations with three-dimensional directional sensitivity in any magnetic field. Applied to a collection of spherical magnetite nanoparticles 9.0 nm in diameter, this enhanced method reveals uniformly canted, magnetically active shells in a nominally saturating field of 1.2 T. The shell thickness depends on temperature, and it disappears altogether when the external field is removed, confirming that these canted nanoparticle shells are magnetic, rather than structural, in origin.
Poly(iohexol) nanoparticles as contrast agents for in vivo X-ray computed tomography imaging.
Yin, Qian; Yap, Felix Y; Yin, Lichen; Ma, Liang; Zhou, Qin; Dobrucki, Lawrence W; Fan, Timothy M; Gaba, Ron C; Cheng, Jianjun
2013-09-18
Biocompatible poly(iohexol) nanoparticles, prepared through cross-linking of iohexol and hexamethylene diisocyanate followed by coprecipitation of the resulting cross-linked polymer with mPEG-polylactide, were utilized as contrast agents for in vivo X-ray computed tomography (CT) imaging. Compared to conventional small-molecule contrast agents, poly(iohexol) nanoparticles exhibited substantially protracted retention within the tumor bed and a 36-fold increase in CT contrast 4 h post injection, which makes it possible to acquire CT images with improved diagnosis accuracy over a broad time frame without multiple administrations.
Kim, Ju-Young; Shim, Sun-Bo; Shim, Jin-Kie
2003-03-17
Micelle-like amphiphilic nano-sized polyurethane (APU) nanoparticles were synthesized via chemical cross-linking reaction of nano-aggregates of urethane acrylate nonionomer (UAN) chain and were tested for extraction efficiency of sorbed phenanthrene from aquifer material. Even though the solubilizing performance and interfacial activity of APU nanoparticles were inferior to that of Triton X-100, in the low concentration region, APU nanoparticles could effectively reduce phenanthrene sorption on the aquifer material and extracted sorbed phenanthrene from the aquifer material, whereas Triton X-100 could not extract sorbed phenanthrene and rather increased phenanthrene sorption onto the aquifer materials. At higher concentrations, APU nanoparticles and Triton X-100 had almost the same soil washing effectiveness. This interesting result is mainly due to a lower degree of sorption of APU nanoparticles onto the aquifer material. The sorption of APU nanoparticles onto aquifer sand is largely hindered by their chemically cross-linked nature, resulting in better soil-washing performance of APU nanoparticles than Triton X-100. Copyright 2003 Elsevier Science B.V.
Chemical and thermal stability of core-shelled magnetite nanoparticles and solid silica
NASA Astrophysics Data System (ADS)
Cendrowski, Krzysztof; Sikora, Pawel; Zielinska, Beata; Horszczaruk, Elzbieta; Mijowska, Ewa
2017-06-01
Pristine nanoparticles of magnetite were coated by solid silica shell forming core/shell structure. 20 nm thick silica coating significantly enhanced the chemical and thermal stability of the iron oxide. Chemical and thermal stability of this structure has been compared to the magnetite coated by mesoporous shell and pristine magnetite nanoparticles. It is assumed that six-membered silica rings in a solid silica shell limit the rate of oxygen diffusion during thermal treatment in air and prevent the access of HCl molecules to the core during chemical etching. Therefore, the core/shell structure with a solid shell requires a longer time to induce the oxidation of iron oxide to a higher oxidation state and, basically, even strong concentrated acid such as HCl is not able to dissolve it totally in one month. This leads to the desired performance of the material in potential applications such as catalysis and environmental protection.
Current advances in precious metal core-shell catalyst design.
Wang, Xiaohong; He, Beibei; Hu, Zhiyu; Zeng, Zhigang; Han, Sheng
2014-08-01
Precious metal nanoparticles are commonly used as the main active components of various catalysts. Given their high cost, limited quantity, and easy loss of catalytic activity under severe conditions, precious metals should be used in catalysts at low volumes and be protected from damaging environments. Accordingly, reducing the amount of precious metals without compromising their catalytic performance is difficult, particularly under challenging conditions. As multifunctional materials, core-shell nanoparticles are highly important owing to their wide range of applications in chemistry, physics, biology, and environmental areas. Compared with their single-component counterparts and other composites, core-shell nanoparticles offer a new active interface and a potential synergistic effect between the core and shell, making these materials highly attractive in catalytic application. On one hand, when a precious metal is used as the shell material, the catalytic activity can be greatly improved because of the increased surface area and the closed interfacial interaction between the core and the shell. On the other hand, when a precious metal is applied as the core material, the catalytic stability can be remarkably improved because of the protection conferred by the shell material. Therefore, a reasonable design of the core-shell catalyst for target applications must be developed. We summarize the latest advances in the fabrications, properties, and applications of core-shell nanoparticles in this paper. The current research trends of these core-shell catalysts are also highlighted.
Thermo-responsive PNIPAM-metal hybrids: An efficient nanocatalyst for the reduction of 4-nitrophenol
NASA Astrophysics Data System (ADS)
Satapathy, Smith Sagar; Bhol, Prachi; Chakkarambath, Aswathy; Mohanta, Jagdeep; Samantaray, Kunal; Bhat, Suresh K.; Panda, Subhendu K.; Mohanty, Priti S.; Si, Satyabrata
2017-10-01
Micron size thermoresponsive cross-linked polymeric microgels of poly(N-isopropylacrylamide) (PNIPAM) are used as "microreactor" for embedding metal nanoparticles of different shapes. Using a simple and robust method, we have synthesized various polymer-metal hybrid nanostructures incorporated with Au nanorods (AuNR), Au nanospheres (AuNS) and Ag nanospheres (AgNS). These hybrid nanostructures have been characterized by transmission electron microscope (TEM), UV-vis spectroscopy, dynamic light scattering (DLS) and static light scattering (SLS) followed by their catalytic activity. TEM studies directly confirmed the mondispersity of synthesized hybrid microgels and stability of the embedded metal nanoparticles within the microgels. Optical studies confirmed the presence of respective absorption bands that correspond to AuNS, AgNS and AuNR respectively. Extensive DLS studies demonstrated that although these hybrid microgels preserve their thermoresponsive properties, i.e their hydrodynamic radius decreased with increasing temperature, their thermosensitivity were comparatively lesser than pure PNIPAM microgels. Combining with studies using static light scattering, we further found that AuNS and AgNS were inhomogeneously distributed within microgels where the majority of the nanoparticles present within the loosely cross-linked shell. On the other hand AuNR were distributed more homogeneously within the microgels. Catalytic performance of various nanostructures loaded onto PNIPAM microgel beads were evaluated by studying the catalytic reduction of 4-nitrophenol. Complete catalytic conversion using AgNS occurred in ∼30 min with a first-order rate constant of 0.159 min-1 having a 7 min induction period. On the other hand no induction period was observed for AuNS and AuNR and the reaction completed in 3-4 min with a first-order rate constant of 1.607 min-1 and 1.627 min-1 respectively. Further, PNIPAM-AuNS and PNIPAM-AuNR possess better catalytic activity as well as recyclability compared to that of PNIPAM-AgNS.
Nitride stabilized core/shell nanoparticles
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kuttiyiel, Kurian Abraham; Sasaki, Kotaro; Adzic, Radoslav R.
Nitride stabilized metal nanoparticles and methods for their manufacture are disclosed. In one embodiment the metal nanoparticles have a continuous and nonporous noble metal shell with a nitride-stabilized non-noble metal core. The nitride-stabilized core provides a stabilizing effect under high oxidizing conditions suppressing the noble metal dissolution during potential cycling. The nitride stabilized nanoparticles may be fabricated by a process in which a core is coated with a shell layer that encapsulates the entire core. Introduction of nitrogen into the core by annealing produces metal nitride(s) that are less susceptible to dissolution during potential cycling under high oxidizing conditions.
Dalvi, Bhagyashree R; Siddiqui, Ejaz A; Syed, Asad S; Velhal, Shilpa M; Ahmad, Absar; Bandivdekar, Atmaram B; Devarajan, Padma V
2016-01-01
HIV/AIDS is a macrophage resident infection localized in the reticuloendothelial system and remote locations of brain and bone marrow. We present core shell nanoparticles of gold(AuNPs) and nevirapine(NVP) for targeted delivery to the multiple HIV reservoirs. The aim of the study was to design core shell NVP loaded AuNPs with high drug loading and to evaluate biodistribution of the nanoparticles in possible HIV reservoirs in vivo. A specific objective was to assess the possible synergy of AuNPs with NVP on anti-HIV activity in vitro. Core shell nanoparticles were prepared by double emulsion solvent evaporation method and characterized. Glyceryl monostearate-nevirapine-gold nanoparticles(GMS-NVP-AuNPs) revealed high entrapment efficiency (>70%), high loading (~40%), particle size <250 nm and zeta potential -35.9± 1.41mv and exhibited sustained release with good stability. Surface plasmon resonance indicated shell formation while SEM coupled EDAX confirmed the presence of Au. TEM confirmed formation of spherical core shell nanoparticles. GMS-NVP-AuNPs revealed low hemolysis (<10 %) and serum stability upto 6 h. GMS-NVP-AuNPs exhibited rapid, high and sustained accumulation in the possible HIV reservoir organs, including the major organs of liver, spleen, lymph nodes, thymus and also remote locations of brain, ovary and bone marrow. High cell viability and enhanced uptake in PBMC's and TZM-bl cells were observed. While uptake in PBMC's proposed monocytes/macrophages enabled brain delivery. GMS-NVP-AuNPs demonstrated synergistic anti-HIV activity. The superior anti-HIV activity in vitro coupled with extensive localization of the nanoparticles in multiple HIV reservoirs suggests great promise of the core shell GMS-NVP-AuNPs for improved therapy of HIV.
Mees, Maarten; Haladjova, Emi; Momekova, Denitsa; Momekov, Georgi; Shestakova, Pavletta S; Tsvetanov, Christo B; Hoogenboom, Richard; Rangelov, Stanislav
2016-11-14
Random copolymers of n-propyl-2-oxazoline and ethylenimine (PPrOx-PEI) were prepared by partial acidic hydrolysis of poly(n-propyl-2-oxazoline) (PPrOx). Dynamic and electrophoretic light scattering and diffusion-ordered NMR spectroscopy were utilized to investigate aqueous solution properties of the copolymers. Above a specific cloud point temperature, well-defined nanoparticles were formed. The latter consisted of a core composed predominantly of PPrOx and a thin positively charged shell from PEI moieties that mediated formation of polyplexes with DNA. The polyplexes were prepared at 65 °C at varying N/P (amine-to-phosphate groups) ratios. They underwent structural changes upon temperature variations 65-25-37 °C depending on N/P. At N/P < 2, the polyplex particles underwent minor changes because of formation of a surface layer of DNA that acted as a barrier and prevented swelling and disintegration of the initial particles. Dramatic rearrangements at N/P ≥ 2 resulting in large swollen microgel particles were overcome by coating of the polyplex particles with a cross-linked polymeric shell. The shell retained the colloidal stability and preserved the physicochemical parameters of the initial polyplex particles while it reduced the high surface potential values. Progressive loss of cytotoxicity upon complexation with DNA and coating of polyplex particles was displayed.
Boyle, Timothy J.; Lu, Ping; Vianco, Paul T.; Chandross, Michael E.
2016-10-11
A nanosolder comprises a first metal nanoparticle core coated with a second metal shell, wherein the first metal has a higher surface energy and smaller atomic size than the second metal. For example, a bimetallic nanosolder can comprise a protective Ag shell "glued" around a reactive Cu nanoparticle. As an example, a 3-D epitaxial Cu-core and Ag-shell structure was generated from a mixture of copper and silver nanoparticles in toluene at temperatures as low as 150.degree. C.
Zhang, Qiaofei; Zhao, Guofeng; Zhang, Zhiqiang; Han, Lupeng; Fan, Songyu; Chai, Ruijuan; Li, Yakun; Liu, Ye; Huang, Jun; Lu, Yong
2016-09-29
A strategy of "macro-micro-nano" organization is reported for embedding oxide-encapsulated-nanoparticles onto monolithic substrates in one-step with the aid of molecularly defined cross-linking agents. Such catalysts, with enhanced heat/mass transfer and high permeability, are qualified for several harsh reaction processes such as CH 4 /VOC abatement, gas-phase hydrogenation of dimethyl oxalate and oxidative dehydrogenation of ethane.
Zhu, Ming; Huang, Xingyi; Yang, Ke; Zhai, Xing; Zhang, Jun; He, Jinliang; Jiang, Pingkai
2014-11-26
The interfacial region plays a critical role in determining the electrical properties and energy storage density of dielectric polymer nanocomposites. However, we still know a little about the effects of electrical properties of the interfacial regions on the electrical properties and energy storage of dielectric polymer nanocomposites. In this work, three types of core-shell structured polymer@BaTiO3 nanoparticles with polymer shells having different electrical properties were used as fillers to prepare ferroelectric polymer nanocomposites. All the polymer@BaTiO3 nanoparticles were prepared by surface-initiated reversible-addition-fragmentation chain transfer (RAFT) polymerization, and the polymer shells were controlled to have the same thickness. The morphology, crystal structure, frequency-dependent dielectric properties, breakdown strength, leakage currents, energy storage capability, and energy storage efficiency of the polymer nanocomposites were investigated. On the other hand, the pure polymers having the same molecular structure as the shells of polymer@BaTiO3 nanoparticles were also prepared by RAFT polymerization, and their electrical properties were provided. Our results show that, to achieve nanocomposites with high discharged energy density, the core-shell nanoparticle filler should simultaneously have high dielectric constant and low electrical conductivity. On the other hand, the breakdown strength of the polymer@BaTiO3-based nanocomposites is highly affected by the electrical properties of the polymer shells. It is believed that the electrical conductivity of the polymer shells should be as low as possible to achieve nanocomposites with high breakdown strength.
Size-tunable drug-delivery capsules composed of a magnetic nanoshell.
Fuchigami, Teruaki; Kitamoto, Yoshitaka; Namiki, Yoshihisa
2012-01-01
Nano-sized FePt capsules with two types of ultrathin shell were fabricated using a template method for use in a nano-scale drug delivery system. One capsule was composed of an inorganic-organic hybrid shell of a water-soluble polymer and FePt nanoparticles, and the other capsule was composed of a network of fused FePt nanoparticles. We demonstrated that FePt nanoparticles selectively accumulated on the polymer molecules adsorbed on the template silica particles, and investigated the morphologies of the particle accumulation by changing the concentration of the polymer solution with which the template particles were treated. Capsular size was reduced from 340 to less than 90 nm by changing the size of the silica template particles, and the shell thickness was controlled by changing the amount of FePt nanoparticles adsorbed on the template particles. The hybrid shell was maintained by the connection of FePt nanoparticles and polymer molecules, and the shell thickness was 10 nm at the maximum. The FePt network shell was fabricated by hydrothermal treatment of the FePt/polymer-modified silica composite particles. The FePt network shell was produced from only the FePt alloy, and the shell thickness was 3 nm. Water-soluble anti-cancer drugs could be loaded into the hollow space of FePt network capsules, and lipid-coated FePt network capsules loaded with anti-cancer drugs showed cellular toxicity. The nano-sized capsular structure and the ultrathin shell suggest applicability as a drug carrier in magnetically guided drug delivery systems.
Size-tunable drug-delivery capsules composed of a magnetic nanoshell
Fuchigami, Teruaki; Kitamoto, Yoshitaka; Namiki, Yoshihisa
2012-01-01
Nano-sized FePt capsules with two types of ultrathin shell were fabricated using a template method for use in a nano-scale drug delivery system. One capsule was composed of an inorganic-organic hybrid shell of a water-soluble polymer and FePt nanoparticles, and the other capsule was composed of a network of fused FePt nanoparticles. We demonstrated that FePt nanoparticles selectively accumulated on the polymer molecules adsorbed on the template silica particles, and investigated the morphologies of the particle accumulation by changing the concentration of the polymer solution with which the template particles were treated. Capsular size was reduced from 340 to less than 90 nm by changing the size of the silica template particles, and the shell thickness was controlled by changing the amount of FePt nanoparticles adsorbed on the template particles. The hybrid shell was maintained by the connection of FePt nanoparticles and polymer molecules, and the shell thickness was 10 nm at the maximum. The FePt network shell was fabricated by hydrothermal treatment of the FePt/polymer-modified silica composite particles. The FePt network shell was produced from only the FePt alloy, and the shell thickness was 3 nm. Water-soluble anti-cancer drugs could be loaded into the hollow space of FePt network capsules, and lipid-coated FePt network capsules loaded with anti-cancer drugs showed cellular toxicity. The nano-sized capsular structure and the ultrathin shell suggest applicability as a drug carrier in magnetically guided drug delivery systems. PMID:23507895
Comparison of antibacterial activities of Ag@TiO2 and Ag@SiO2 core-shell nanoparticles
NASA Astrophysics Data System (ADS)
Dhanalekshmi, K. I.; Meena, K. S.
2014-07-01
Core-shell type Ag@TiO2 nanoparticles were prepared by one pot simultaneous reduction of AgNO3 and hydrolysis of Ti (IV) isopropoxide and Ag@SiO2 core-shell nanoparticles were prepared by Stober's method. They were characterized by absorption, XRD, and HR-TEM techniques. XRD patterns show the presence of anatase form of TiO2 and amorphous form of SiO2 and the noble metal (Ag). High resolution transmission electron microscopy measurements revealed that their size is below 50 nm. The antibacterial properties of Ag@TiO2 and Ag@SiO2 core-shell nanoparticles against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were examined by the agar diffusion method. As a result E. coli and S. aureus were shown to be substantially inhibited by Ag@TiO2 and Ag@SiO2 core-shell nanoparticles. These results demonstrated that TiO2 and SiO2 supported on the surface of Ag NPs without aggregation was proved to have enhanced antibacterial activity.
Comparison of antibacterial activities of Ag@TiO2 and Ag@SiO2 core-shell nanoparticles.
Dhanalekshmi, K I; Meena, K S
2014-07-15
Core-shell type Ag@TiO2 nanoparticles were prepared by one pot simultaneous reduction of AgNO3 and hydrolysis of Ti (IV) isopropoxide and Ag@SiO2 core-shell nanoparticles were prepared by Stober's method. They were characterized by absorption, XRD, and HR-TEM techniques. XRD patterns show the presence of anatase form of TiO2 and amorphous form of SiO2 and the noble metal (Ag). High resolution transmission electron microscopy measurements revealed that their size is below 50 nm. The antibacterial properties of Ag@TiO2 and Ag@SiO2 core-shell nanoparticles against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were examined by the agar diffusion method. As a result E. coli and S. aureus were shown to be substantially inhibited by Ag@TiO2 and Ag@SiO2 core-shell nanoparticles. These results demonstrated that TiO2 and SiO2 supported on the surface of Ag NPs without aggregation was proved to have enhanced antibacterial activity. Copyright © 2014 Elsevier B.V. All rights reserved.
Novel highly ordered core–shell nanoparticles
DOE Office of Scientific and Technical Information (OSTI.GOV)
Dey, Sonal; Hossain, Mohammad D.; Mayanovic, Robert A.
2016-10-26
Core–shell nanoparticles have potential for a wide range of applications due to the tunability of their magnetic, catalytic, electronic, optical, and other physicochemical properties. A frequent drawback in the design of core–shell nanoparticles and nanocrystals is the lack of control over an extensive, disordered, and compositionally distinct interface that occurs due to the dissimilarity of structural and compositional phases of the core and shell. In this work, we demonstrate a new hydrothermal nanophase epitaxy (HNE) technique to synthesize highly structurally ordered α-Cr 2O 3@α-Co 0.38Cr 1.62O 2.92 inverted core–shell nanoparticles (CSNs) with evidence for the nanoscale growth of corundum structuremore » beginning from the core and extending completely into the shell of the CSNs with minimal defects at the interface. The high-resolution TEM results show a sharp interface exhibiting epitaxial atomic registry of shell atoms over highly ordered core atoms. The XPS and Co K-edge XANES analyses indicate the +2 oxidation state of cobalt is incorporated in the shell of the CSNs. Our XPS and EXAFS results are consistent with oxygen vacancy formation in order to maintain charge neutrality upon substitution of the Co 2+ ion for the Cr 3+ ion in the α-Co 0.38Cr 1.62O 2.92 shell. Furthermore, the CSNs exhibit the magnetic exchange bias effect, which is attributed to the exchange anisotropy at the interface made possible by the nanophase epitaxial growth of the α-Co 0.38Cr 1.62O 2.92 shell on the α-Cr 2O 3 core of the nanoparticles. The combination of a well-structured, sharp interface and novel nanophase characteristics is highly desirable for nanostructures having enhanced magnetic properties.« less
Multimodality Imaging with Silica-Based Targeted Nanoparticle Platforms
DOE Office of Scientific and Technical Information (OSTI.GOV)
Jason S. Lewis
2012-04-09
Objectives: To synthesize and characterize a C-Dot silica-based nanoparticle containing 'clickable' groups for the subsequent attachment of targeting moieties (e.g., peptides) and multiple contrast agents (e.g., radionuclides with high specific activity) [1,2]. These new constructs will be tested in suitable tumor models in vitro and in vivo to ensure maintenance of target-specificity and high specific activity. Methods: Cy5 dye molecules are cross-linked to a silica precursor which is reacted to form a dye-rich core particle. This core is then encapsulated in a layer of pure silica to create the core-shell C-Dot (Figure 1) [2]. A 'click' chemistry approach has beenmore » used to functionalize the silica shell with radionuclides conferring high contrast and specific activity (e.g. 64Cu and 89Zr) and peptides for tumor targeting (e.g. cRGD and octreotate) [3]. Based on the selective Diels-Alder reaction between tetrazine and norbornene, the reaction is bioorthogonal, highyielding, rapid, and water-compatible. This radiolabeling approach has already been employed successfully with both short peptides (e.g. octreotate) and antibodies (e.g. trastuzumab) as model systems for the ultimate labeling of the nanoparticles [1]. Results: PEGylated C-Dots with a Cy5 core and labeled with tetrazine have been synthesized (d = 55 nm, zeta potential = -3 mV) reliably and reproducibly and have been shown to be stable under physiological conditions for up to 1 month. Characterization of the nanoparticles revealed that the immobilized Cy5 dye within the C-Dots exhibited fluorescence intensities over twice that of the fluorophore alone. The nanoparticles were successfully radiolabeled with Cu-64. Efforts toward the conjugation of targeting peptides (e.g. cRGD) are underway. In vitro stability, specificity, and uptake studies as well as in vivo imaging and biodistribution investigations will be presented. Conclusions: C-Dot silica-based nanoparticles offer a robust, versatile, and multi-functional platform to enhance in vivo detection sensitivity and non-invasively assay receptor expression/status of tumor cellular targets, including those of low abundance, using nuclear-NIR fluorescence imaging approaches [2]. Improvements in molecular diagnostics, refined by the availability of nanotechnology platforms, will be a key determinant in driving early-stage disease detection and prevention, ultimately leading to decreases in mortality.« less
Ren, Xiuyan; Huang, Chang; Duan, Lijie; Liu, Baijun; Bu, Lvjun; Guan, Shuang; Hou, Jiliang; Zhang, Huixuan; Gao, Guanghui
2017-05-14
Toughness, strechability and compressibility for hydrogels were ordinarily balanced for their use as mechanically responsive materials. For example, macromolecular microsphere composite hydrogels with chemical crosslinking exhibited excellent compression strength and strechability, but poor tensile stress. Here, a novel strategy for the preparation of a super-tough, ultra-stretchable and strongly compressive hydrogel was proposed by introducing core-shell latex particles (LPs) as crosslinking centers for inducing efficient aggregation of hydrophobic chains. The core-shell LPs always maintained a spherical shape due to the presence of a hard core even by an external force and the soft shell could interact with hydrophobic chains due to hydrophobic interactions. As a result, the hydrogels reinforced by core-shell LPs exhibited not only a high tensile strength of 1.8 MPa and dramatic elongation of over 20 times, but also an excellent compressive performance of 13.5 MPa at a strain of 90%. The Mullins effect was verified for the validity of core-shell LP-reinforced hydrogels by inducing aggregation of hydrophobic chains. The novel strategy strives to provide a better avenue for designing and developing a new generation of hydrophobic association tough hydrogels with excellent mechanical properties.
Multifunctional magnetic and fluorescent core-shell nanoparticles for bioimaging.
Lu, Yanjiao; He, Bicheng; Shen, Jie; Li, Jie; Yang, Wantai; Yin, Meizhen
2015-02-07
Novel magnetic and fluorescent core-shell nanoparticles have been fabricated, which exhibit superparamagnetic behavior and emit strong near-infrared fluorescence. The nanoparticles are highly biocompatible and can be internalized into cells with nucleic accumulation via strong interaction with nucleic acids, implying potential applications in the biomedical field.
Deposition of conductive TiN shells on SiO2 nanoparticles with a fluidized bed ALD reactor
NASA Astrophysics Data System (ADS)
Didden, Arjen; Hillebrand, Philipp; Wollgarten, Markus; Dam, Bernard; van de Krol, Roel
2016-02-01
Conductive TiN shells have been deposited on SiO2 nanoparticles (10-20 nm primary particle size) with fluidized bed atomic layer deposition using TDMAT and NH3 as precursors. Analysis of the powders confirms that shell growth saturates at approximately 0.4 nm/cycle at TDMAT doses of >1.2 mmol/g of powder. TEM and XPS analysis showed that all particles were coated with homogeneous shells containing titanium. Due to the large specific surface area of the nanoparticles, the TiN shells rapidly oxidize upon exposure to air. Electrical measurements show that the partially oxidized shells are conducting, with apparent resistivity of approximately 11 kΩ cm. The resistivity of the powders is strongly influenced by the NH3 dose, with a smaller dose giving an order-of-magnitude higher resistivity.
Effect of core-shell structure on optical properties of Au-Cu2O nanoparticles
NASA Astrophysics Data System (ADS)
Sai, Cong Doanh; Ngac, An Bang
2018-03-01
Solid Au-Cu2O core-shell nanoparticles were synthesized using gold nanoparticles of 16.6 nm in size as the core. The core-shell structure of the synthesized particles was confirmed and characterized by TEM and HRTEM images. Due to their similar crystal structure, the (111) planes of Cu2O are nucleated and grown epitaxially on the {111} facets of Au nanoparticles with the lattice mismatch of about 4.3% resulting in a polycrystallized Cu2O shell covering the Au nanocore. Due to the quantum confinement effect, the band gap energy Eg of the synthesized Cu2O shells is blue-shifted from 2.35 to 2.70 eV as the shell thickness decreases from of 24.6±3.6 to 9.0±1.7 nm. The localized SPR (Surface Plasmon Resonance) peak of the Au nanocore undergoes a large red shift of the order of a hundred of nm due to both the high refractive index and the increase of the thickness of Cu2O shell. Theoretical models within the Drude framework significantly underestimate the experimental data and predict a wrong rate of change of the SPR peak position with respect to the shell thickness.
Li, Yanan; Jin, Chenjing; Yuan, Ganyin; Han, Jie; Wang, Minggui; Guo, Rong
2017-08-01
Multifunctional nanocatalysts of Au@Fe 3 O 4 /m-SiO 2 yolk@shell hybrids had been developed through a template-assisted synthesis, where Fe 3 O 4 nanoparticles (∼12 nm) and m-SiO 2 shells were sequentially assembled on surfaces of Au/SiO 2 core/shell templates, followed by selective etching of the inner SiO 2 cores, leading to the formation of Au@Fe 3 O 4 /m-SiO 2 yolk@shell hybrids. The Fe 3 O 4 nanoparticles were implanted in the inner surfaces of m-SiO 2 shells with partially exposed surfaces to the inner cavity. The novel design not only ensures a high surface area (540.0 m 2 /g) and saturation magnetization (48.6 emu/g) of the hybrids but also enables interaction between Au and Fe 3 O 4 nanoparticles. Catalytic tests toward the reduction of 4-nitrophenol in the presence of NaBH 4 indicated that Au@Fe 3 O 4 /m-SiO 2 yolk@shell nanocatalysts not only showed high stability and recyclability but also maintained improved catalytic activity as a result of the synergetic effect resulting from Au and Fe 3 O 4 interactions.
NASA Astrophysics Data System (ADS)
Li, Jie; Tan, Li; Wang, Ge; Yang, Mu
2015-03-01
Double-shelled sea urchin-like yolk-shell Fe3O4/TiO2/Au microspheres were successfully synthesized through loading Au nanoparticles on the Fe3O4/TiO2 support by a in situ reduction of HAuCl4 with NaBH4 aqueous solution. These microspheres possess tunable cavity size, adjustable shell layers, high structural stability and large specific surface area. The Au nanoparticles of approximately 5 nm in diameter were loaded both on the TiO2 nanofibers and inside the cavities of sea urchin-like yolk-shell Fe3O4/TiO2 microspheres. The sea urchin-like structure composed of TiO2 nanofibers ensure the good distribution of the Au nanoparticles, while the novel double-shelled yolk-shell structure guarantees the high stability of the Au nanoparticles. Furthermore, the Fe3O4 magnetic core facilitates the convenient recovery of the catalyst by applying an external magnetic field. The Fe3O4/TiO2/Au microspheres display excellent activities and recycling properties in the catalytic reduction of 4-nitrophenol (4-NP): the rate constant is 1.84 min-1 and turnover frequency is 5457 h-1.
UV-VIS extinction spectra of gold particle coated by oligonucleotide shell
NASA Astrophysics Data System (ADS)
Bogatyrev, Vladimir A.; Vrublevsky, Stanislav A.; Trachuk, Lyubov A.; Khlebtsov, Nikolai G.
2005-06-01
We describe synthesis process of an oligonucleotide-functionalized colloidal gold marker CG-l5-T28, its optical properties and interaction with poly(A) in solution and on a solid-phase substrate. The marker is a complex of 15 nm diameter colloidal gold nanoparticles with covalently attached 5'-thiolated 28-base oligothymidine macromolecules. A positive hybridization reaction of the marker with poly(A) is observed by solid-phase analysis on hanging a spot color (from red to blue ) or on appearance of a red dye in dot-blot test as compared to control experiments with poly(U) target. The principles of spectrophotometric monitoring all stages of the marker preparation and application of spectrophotometry to detection of the polynucleotide hybridization in vitro are described. Experimental data were compared with theoretical calculations based on Mie theory for 2-layer model of gold core in polymeric shell with imaginary part of refractive index that typical for the real absorption spectra of NA. To explain the aggregation of CG-15-T28 caused by interaction with poly(A) in solution, we suggest a new model differing from a standard model of cross-linker binding.
Hydrogen sorption in Pd-decorated Mg-MgO core-shell nanoparticles
NASA Astrophysics Data System (ADS)
Callini, E.; Pasquini, L.; Piscopiello, E.; Montone, A.; Antisari, M. Vittori; Bonetti, E.
2009-06-01
Mg nanoparticles with metal-oxide core-shell morphology were synthesized by inert-gas condensation and decorated by in situ Pd deposition. Transmission electron microscopy and x-ray diffraction underline the formation of a noncontinuous layer with Pd clusters on top of the MgO shell. Even in the presence of a thick MgO interlayer, a modest (2 at. %) Pd decoration deeply enhances the hydrogen sorption properties: previously inert nanoparticles exhibit metal-hydride transformation with fast kinetics and gravimetric capacity above 5 wt %.
NASA Astrophysics Data System (ADS)
Hikmah, N.; Idrus, N. F.; Jai, J.; Hadi, A.
2016-06-01
Silver and copper nanoparticles are well-known as the good antimicrobial agent. The nano-size of particles influences in enhancing the antimicrobial activity. This paper discusses the effect of molarity on the microstructure and morphology of silver-copper core-shell nanoparticles prepared by a polyol method. In this study, silver-copper nanoparticles are synthesized through the green approach of polyol method using ethylene glycol (EG) as green solvent and reductant, and polyoxyethylene-(80)-sorbitan monooleate (Tween 80) as a nontoxic stabilizer. The phase and morphology of silver-copper nanoparticles are characterized by X-ray diffraction (XRD) and Field emission scanning electron microscope (FESEM) and Transmission electron microscope (TEM). The results XRD confirm the pure crystalline of silver and copper nanoparticles with face-centered cubic (FCC) structure. FESEM and TEM analysis confirm the existence of Ag and Cu nanoparticles in core-shell shape.
Synthesis of robust water-soluble ZnS:Mn/SiO2 core/shell nanoparticles
NASA Astrophysics Data System (ADS)
Sun, Jing; Zhuang, Jiaqi; Guan, Shaowei; Yang, Wensheng
2008-04-01
Water-soluble Mn doped ZnS (ZnS:Mn) nanocrystals synthesized by using 3-mercaptopropionic acid (MPA) as stabilizer were homogeneously coated with a dense silica shell through a multi-step procedure. First, 3-mercaptopropyl triethoxy silane (MPS) was used to replace MPA on the particle surface to form a vitreophilic layer for further silica deposition under optimal experimental conditions. Then a two-step silica deposition was performed to form the final water-soluble ZnS:Mn/SiO2 core/shell nanoparticles. The as-prepared core/shell nanoparticles show little change in fluorescence intensity in a wide range of pH value.
Structural analysis of Fe–Mn–O nanoparticles in glass ceramics by small angle scattering
DOE Office of Scientific and Technical Information (OSTI.GOV)
Raghuwanshi, Vikram Singh, E-mail: vikram.raghuwanshi@helmholtz-berlin.de; Harizanova, Ruzha; Tatchev, Dragomir
2015-02-15
Magnetic nanocrystals containing Fe and Mn were obtained by annealing of silicate glasses with the composition 13.6Na{sub 2}O–62.9SiO{sub 2}–8.5MnO–15.0Fe{sub 2}O{sub 3−x} (mol%) at 580 °C for different periods of time. Here, we present Small Angle Neutron Scattering using Polarized neutrons (SANSPOL) and Anomalous Small Angle X-ray Scattering (ASAXS) investigation on these glass ceramic samples. Analysis of scattering data from both methods reveals the formation of spherical core–shell type of nanoparticles with mean sizes between 10 nm and 100 nm. ASAXS investigation shows the particles have higher concentration of iron atoms and the shell like region surrounding the particles is enrichedmore » in SiO{sub 2}. SANSPOL investigation shows the particles are found to be magnetic and are surrounded by a non-magnetic shell-like region. - Graphical abstract: Magnetic spherical core–shell nanoparticles in glass ceramics: SANSPOL and ASAXS investigations. - Highlights: • Formation and growth mechanisms of magnetic nanoparticles in silicate glass. • SANSPOL and ASAXS methods employed to evaluate quantitative information. • Analyses showed formation of nanoparticles with spherical core–shell structures. • Core of the particle is magnetic and surrounded by weak magnetic shell like region.« less
Ogunwuyi, O; Adesina, S; Akala, E O
2015-03-01
We report here our efforts on the development of stealth biodegradable crosslinked poly-ε-caprolactone nanoparticles by free radical dispersion polymerization suitable for the delivery of bioactive agents. The uniqueness of the dispersion polymerization technique is that it is surfactant free, thereby obviating the problems known to be associated with the use of surfactants in the fabrication of nanoparticles for biomedical applications. Aided by a statistical software for experimental design and analysis, we used D-optimal mixture statistical experimental design to generate thirty batches of nanoparticles prepared by varying the proportion of the components (poly-ε-caprolactone macromonomer, crosslinker, initiators and stabilizer) in acetone/water system. Morphology of the nanoparticles was examined using scanning electron microscopy (SEM). Particle size and zeta potential were measured by dynamic light scattering (DLS). Scheffe polynomial models were generated to predict particle size (nm) and particle surface zeta potential (mV) as functions of the proportion of the components. Solutions were returned from simultaneous optimization of the response variables for component combinations to (a) minimize nanoparticle size (small nanoparticles are internalized into disease organs easily, avoid reticuloendothelial clearance and lung filtration) and (b) maximization of the negative zeta potential values, as it is known that, following injection into the blood stream, nanoparticles with a positive zeta potential pose a threat of causing transient embolism and rapid clearance compared to negatively charged particles. In vitro availability isotherms show that the nanoparticles sustained the release of docetaxel for 72 to 120 hours depending on the formulation. The data show that nanotechnology platforms for controlled delivery of bioactive agents can be developed based on the nanoparticles.
Magnetocapacitance effect in core/shell NiO nanoparticles
NASA Astrophysics Data System (ADS)
Roy, Subir; Kambhala, Nagaiah; Angappane, S.
2018-04-01
The exchange bias and magnetocapacitance properties of nickel oxide nanoparticles of average particle size 50 nm have been studied. NiO nanoparticles of uniform size distribution were synthesized by a sol-gel method using nickel acetate and polyvinyl acetate. The magnetic measurements show the ferromagnetic like behavior exhibiting exchange bias effect indicative of the formation of core/shell structure of NiO with a antiferromagnetic core and ferromagnetic shell. An electrical double layer capacitance behavior was observed for NiO nanoparticles in the cyclic voltammetry measurement, and it was found that the value of capacitance decreased by about 26 % under the application of magnetic field of 0.1 T.
Wang, Yi; Wei, Guoqing; Zhang, Xiaobin; Huang, Xuehui; Zhao, Jingya; Guo, Xing; Zhou, Shaobing
2018-03-01
Mitochondrial-targeting therapy is an emerging strategy for enhanced cancer treatment. In the present study, a multistage targeting strategy using doxorubicin-loaded magnetic composite nanoparticles is developed for enhanced efficacy of photothermal and chemical therapy. The nanoparticles with a core-shell-SS-shell architecture are composed of a core of Fe 3 O 4 colloidal nanocrystal clusters, an inner shell of polydopamine (PDA) functionalized with triphenylphosphonium (TPP), and an outer shell of methoxy poly(ethylene glycol) linked to the PDA by disulfide bonds. The magnetic core can increase the accumulation of nanoparticles at the tumor site for the first stage of tumor tissue targeting. After the nanoparticles enter the tumor cells, the second stage of mitochondrial targeting is realized as the mPEG shell is detached from the nanoparticles by redox responsiveness to expose the TPP. Using near-infrared light irradiation at the tumor site, a photothermal effect is generated from the PDA photosensitizer, leading to a dramatic decrease in mitochondrial membrane potential. Simultaneously, the loaded doxorubicin can rapidly enter the mitochondria and subsequently damage the mitochondrial DNA, resulting in cell apoptosis. Thus, the synergism of photothermal therapy and chemotherapy targeting the mitochondria significantly enhances the cancer treatment. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Wang, Yaokun; Yan, Mingyang
2017-01-01
Hierarchical copper shells anchored on magnetic nanoparticles were designed and fabricated to selectively deplete hemoglobin from human blood by immobilized metal affinity chromatography. Briefly, CoFe2O4 nanoparticles coated with polyacrylic acid were first synthesized by a one-pot solvothermal method. Hierarchical copper shells were then deposited by immobilizing Cu2+ on nanoparticles and subsequently by reducing between the solid CoFe2O4@COOH and copper solution with NaBH4. The resulting nanoparticles were characterized by scanning electron microscopy, transmission electron microscopy, Fourier transform infrared spectrometry, X-ray photoelectron spectroscopy, and vibrating sample magnetometry. The particles were also tested against purified bovine hemoglobin over a range of pH, contact time, and initial protein concentration. Hemoglobin adsorption followed pseudo-second-order kinetics and reached equilibrium in 90 min. Isothermal data also fit the Langmuir model well, with calculated maximum adsorption capacity 666 mg g−1. Due to the high density of Cu2+ on the shell, the nanoparticles efficiently and selectively deplete hemoglobin from human blood. Taken together, the results demonstrate that the particles with hierarchical copper shells effectively remove abundant, histidine-rich proteins, such as hemoglobin from human blood, and thereby minimize interference in diagnostic and other assays. PMID:28316987
Suresh, S; Saravanan, P; Jayamoorthy, K; Ananda Kumar, S; Karthikeyan, S
2016-07-01
In this article a series of epoxy nanocomposites film were developed using amine functionalized (ZnO-APTES) core shell nanoparticles as the dispersed phase and a commercially available epoxy resin as the matrix phase. The functional group of the samples was characterized using FT-IR spectra. The most prominent peaks of epoxy resin were found in bare epoxy and in all the functionalized ZnO dispersed epoxy nanocomposites (ZnO-APTES-DGEBA). The XRD analysis of all the samples exhibits considerable shift in 2θ, intensity and d-spacing values but the best and optimum concentration is found to be 3% ZnO-APTES core shell nanoparticles loaded epoxy nanocomposites supported by FT-IR results. From TGA measurements, 100wt% residue is obtained in bare ZnO nanoparticles whereas in ZnO core shell nanoparticles grafted DGEBA residue percentages are 37, 41, 45, 46 and 52% for 0, 1, 3, 5 and 7% ZnO-APTES-DGEBA respectively, which is confirmed with ICP-OES analysis. From antimicrobial activity test, it was notable that antimicrobial activity of 7% ZnO-APTES core shell nanoparticles loaded epoxy nanocomposite film has best inhibition zone effect against all pathogens under study. Copyright © 2016 Elsevier B.V. All rights reserved.
Dong, Yanrui; Xiao, Congming
2017-09-01
Facile and mild ionic cross-linking and freezing/thawing technologies were applied to prepare double strengthened core-shell particles by using water-soluble chitosan (WSC), sodium alginate (SA) and poly(vinyl alcohol) (PVA) as starting materials. The aqueous solution contained WSC and PVA was dropped in ethanol to form beads. The beads were converted into WSC/PVA hydrogel particles by being subjected to three freeze/thaw cycles. Subsequently, ionic cross-linked hydrogel layer was formed around each WSC/PVA particle to generate core-shell particulates. Fourier transform infrared spectra confirmed the combination among various components. Dynamic mechanical thermal analysis indicated that the storage modulus of the core-shell hydrogel was improved obviously. Thermogravimetric analysis exhibited the thermal stability of the particles was also enhanced by incorporation of PVA. It was found that the particles were able to adsorb carbon dioxide, lead ion and copper ion. The adsorption capacities of dry particles toward carbon dioxide, Pb(II) and Cu(II) could reach 199.62, 39.28 and 26.03mg/g, respectively. The rates of the particles for binding Pb(II) and Cu(II) at initial stage were 26.57 and 4.30%/min, respectively. These experimental results suggested that the particles were an efficient sorbent for removing hazardous substances such as carbon dioxide and heavy-metal ions. Copyright © 2017 Elsevier B.V. All rights reserved.
Zhang, Jianling; Liu, Zhimin; Han, Buxing; Li, Junchun; Li, Zhonghao; Yang, Guanying
2005-06-01
In this work, a route for the synthesis of inorganic/polymer core/shell composite nanoparticles was proposed, which can be called the antisolvent-ultrasound method. Compressed CO2 was used as antisolvent to precipitate the polymer from its solution dispersed with inorganic nanoparticles, during which ultrasonic irradiation was used to induce the coating of precipitated polymers on the surfaces of the inorganic nanoparticles. TiO2/polystyrene (PS) core/shell nanocomposites have been successfully prepared using this method. The transmission electronic micrographs (TEM) of the obtained nanocomposites show that the TiO2 nanoparticles are coated by the PS shells, of which the thickness can be tuned by the pressure of CO2. The phase structure, absorption properties, and thermal stability of the composite were characterized by X-ray diffraction (XRD), UV-vis spectra, and thermogravimetry, respectively. The results of X-ray photoelectron spectra (XPS) indicate the formation of a strong interaction between PS and TiO2 nanoparticles in the resultant products. This method has some potential advantages for applications and may be easily applied to the preparation of a range of inorganic/polymer core/shell composite nanoparticles.
Electrosprayed nanoparticle delivery system for controlled release.
Eltayeb, Megdi; Stride, Eleanor; Edirisinghe, Mohan; Harker, Anthony
2016-09-01
This study utilises an electrohydrodynamic technique to prepare core-shell lipid nanoparticles with a tunable size and high active ingredient loading capacity, encapsulation efficiency and controlled release. Using stearic acid and ethylvanillin as model shell and active ingredients respectively, we identify the processing conditions and ratios of lipid:ethylvanillin required to form nanoparticles. Nanoparticles with a mean size ranging from 60 to 70nm at the rate of 1.37×10(9) nanoparticles per minute were prepared with different lipid:ethylvanillin ratios. The polydispersity index was ≈21% and the encapsulation efficiency ≈70%. It was found that the rate of ethylvanillin release was a function of the nanoparticle size, and lipid:ethylvanillin ratio. The internal structure of the lipid nanoparticles was studied by transmission electron microscopy which confirmed that the ethylvanillin was encapsulated within a stearic acid shell. Fourier transform infrared spectroscopy analysis indicated that the ethylvanillin had not been affected. Extensive analysis of the release of ethylvanillin was performed using several existing models and a new diffusive release model incorporating a tanh function. The results were consistent with a core-shell structure. Copyright © 2016 Elsevier B.V. All rights reserved.
Pacheco-Salazar, O F; Wakayama, Shuichi; Sakai, Takenobu; Cauich-Rodríguez, J V; Ríos-Soberanis, C R; Cervantes-Uc, J M
2015-06-01
In this work, the effect of the incorporation of core-shell particles on the fracture mechanisms of the acrylic bone cements by using acoustic emission (AE) technique during the quasi-static compression mechanical test was investigated. Core-shell particles were composed of a poly(butyl acrylate) (PBA) rubbery core and a methyl methacrylate/styrene copolymer (P(MMA-co-St)) outer glassy shell. Nanoparticles were prepared with different core-shell ratio (20/80, 30/70, 40/60 and 50/50) and were incorporated into the solid phase of bone cement at several percentages (5, 10 and 15 wt%). It was observed that the particles exhibited a spherical morphology averaging ca. 125 nm in diameter, and the dynamic mechanical analysis (DMA) thermograms revealed the desired structuring pattern of phases associated with core-shell structures. A fracture mechanism was proposed taking into account the detected AE signals and the scanning electron microscopy (SEM) micrographs. In this regard, core-shell nanoparticles can act as both additional nucleation sites for microcracks (and crazes) and to hinder the microcrack propagation acting as a barrier to its growth; this behavior was presented by all formulations. Cement samples containing 15 wt% of core-shell nanoparticles, either 40/60 or 50/50, were fractured at 40% deformation. This fact seems related to the coalescence of microcracks after they surround the agglomerates of core-shell nanoparticles to continue growing up. This work also demonstrated the potential of the AE technique to be used as an accurate and reliable detection tool for quasi-static compression test in acrylic bone cements. Copyright © 2015 Elsevier Ltd. All rights reserved.
Li, Xue; Niitsoo, Olivia; Couzis, Alexander
2016-03-01
An electrostatically-assisted strategy for fabrication of thin film composite capacitors with controllable dielectric constant (k) has been developed. The capacitor is composed of metal-dielectric core/shell nanoparticle (silver/silica, Ag@SiO2) multilayer films, and a backfilling polymer. Compared with the simple metal particle-polymer mixtures where the metal nanoparticles (NP) are randomly dispersed in the polymer matrix, the metal volume fraction in our capacitor was significantly increased, owing to the densely packed NP multilayers formed by the electrostatically assisted assembly process. Moreover, the insulating layer of silica shell provides a potential barrier that reduces the tunneling current between neighboring Ag cores, endowing the core/shell nanocomposites with a stable and relatively high dielectric constant (k) and low dielectric loss (D). Our work also shows that the thickness of the SiO2 shell plays a dominant role in controlling the dielectric properties of the nanocomposites. Control over metal NP separation distance was realized not only by variation the shell thickness of the core/shell NPs but also by introducing a high k nanoparticle, barium strontium titanate (BST) of relatively smaller size (∼8nm) compared to 80-160nm of the core/shell Ag@SiO2 NPs. The BST assemble between the Ag@SiO2 and fill the void space between the closely packed core/shell NPs leading to significant enhancement of the dielectric constant. This electrostatically assisted assembly method is promising for generating multilayer films of a large variety of NPs over large areas at low cost. Copyright © 2015 Elsevier Inc. All rights reserved.
Li, Wei-Peng; Liao, Pei-Yi; Su, Chia-Hao; Yeh, Chen-Sheng
2014-07-16
A new multifunctional nanoparticle to perform a near-infrared (NIR)-responsive remote control drug release behavior was designed for applications in the biomedical field. Different from the previous studies in formation of Fe3O4-Au core-shell nanoparticles resulting in a spherical morphology, the heterostructure with polyhedral core and shell was presented with the truncated octahedral Fe3O4 nanoparticle as the core over a layer of trisoctahedral Au shell. The strategy of Fe3O4@polymer@Au was adopted using poly-l-lysine as the mediate layer, followed by the subsequent seeded growth of Au nanoparticles to form a Au trisoctahedral shell. Fe3O4@Au trisoctahedra possess high-index facets of {441}. To combine photothermal and chemotherapy in a remote-control manner, the trisoctahedral core-shell Fe3O4@Au nanoparticles were further covered with a mesoporous silica shell, yielding Fe3O4@Au@mSiO2. The bondable oligonucleotides (referred as dsDNA) were used as pore blockers of the mesoporous silica shell that allowed the controlled release, resulting in a NIR-responsive DNA-gated Fe3O4@Au@mSiO2 nanocarrier. Taking advantage of the magnetism, remotely triggered drug release was facilitated by magnetic attraction accompanied by the introduction of NIR radiation. DNA-gated Fe3O4@Au@mSiO2 serves as a drug control and release carrier that features functions of magnetic target, MRI diagnosis, and combination therapy through the manipulation of a magnet and a NIR laser. The results verified the significant therapeutic effects on tumors with the assistance of combination therapy consisting of magnetic guidance and remote NIR control.
Process to make core-shell structured nanoparticles
Luhrs, Claudia; Phillips, Jonathan; Richard, Monique N
2014-01-07
Disclosed is a process for making a composite material that contains core-shell structured nanoparticles. The process includes providing a precursor in the form of a powder a liquid and/or a vapor of a liquid that contains a core material and a shell material, and suspending the precursor in an aerosol gas to produce an aerosol containing the precursor. In addition, the process includes providing a plasma that has a hot zone and passing the aerosol through the hot zone of the plasma. As the aerosol passes through the hot zone of the plasma, at least part of the core material and at least part of the shell material in the aerosol is vaporized. Vapor that contains the core material and the shell material that has been vaporized is removed from the hot zone of the plasma and allowed to condense into core-shell structured nanoparticles.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kuttiyiel, Kurian A.; Sasaki, Kotaro; Adzic, Radoslav R.
Embodiments of the disclosure relate to intermetallic nanoparticles. Embodiments include nanoparticles having an intermetallic core including a first metal and a second metal. The first metal may be palladium and the second metal may be at least one of cobalt, iron, nickel, or a combination thereof. The nanoparticles may further have a shell that includes palladium and gold.
Nanoparticle Delivery of RNAi Therapeutics for Ocular Vesicant Injury
2014-04-01
nanoparticles to smaller size with higher stability in physiological media, optimized a protocol to surface-coat nucleic acid nanoparticles with hyaluronic acid ...nanoparticle tissue retention and cell uptake by conjugating cell adhesion ligand to nanoparticles and by surface coating of hyaluronic acid to... hyaluronic acid , and retain the stability of the nanoparticles. Identified the conditions using reversible crosslinking density to stabilize siRNA
Synthesis of core-shell iron nanoparticles via a new (novel) approach
NASA Astrophysics Data System (ADS)
Chaudhary, Rakesh P.; Koymen, Ali R.
2014-03-01
Carbon-encapsulated iron (Fe) nanoparticles were synthesized by a newly developed method in toluene. Transmission Electron Microscopy (TEM) and High Resolution Transmission Electron Microscopy (HRTEM) of the as prepared sample reveal that core-shell nanostructures have been formed with Fe as core and graphitic carbon as shell. Fe nanoparticles with diameter 11nm to 102 nm are encapsulated by 6-8 nm thick graphitic carbon layers. There was no iron carbide formation observed between the Fe core and the graphitic shell. The Fe nanoparticles have body centered cubic (bcc) crystal structure. The magnetic hysteresis loop of the as synthesized powder at room temperature showed a saturation magnetization of 9 Am2 kg-1. After thermal treatment crystalline order of the samples improved and hence saturation magnetization increased to 24 Am2kg-1. We foresee that the carbon-encapsulated Fe nanoparticles are biologically friendly and could have potential applications in Magnetic Resonance Imaging (MRI) and Photothermal cancer therapy.
Synthesis and Luminescence Properties of Core/Shell ZnS:Mn/ZnO Nanoparticles.
Jiang, Daixun; Cao, Lixin; Liu, Wei; Su, Ge; Qu, Hua; Sun, Yuanguang; Dong, Bohua
2009-01-01
In this paper the influence of ZnO shell thickness on the luminescence properties of Mn-doped ZnS nanoparticles is studied. Transmission electron microscopy (TEM) images showed that the average diameter of ZnS:Mn nanoparticles is around 14 nm. The formation of ZnO shells on the surface of ZnS:Mn nanoparticles was confirmed by X-ray diffraction (XRD) patterns, high-resolution TEM (HRTEM) images, and X-ray photoelectron spectroscopy (XPS) measurements. A strong increase followed by a gradual decline was observed in the room temperature photoluminescence (PL) spectra with the thickening of the ZnO shell. The photoluminescence excitation (PLE) spectra exhibited a blue shift in ZnO-coated ZnS:Mn nanoparticles compared with the uncoated ones. It is shown that the PL enhancement and the blue shift of optimum excitation wavelength are led by the ZnO-induced surface passivation and compressive stress on the ZnS:Mn cores.
Synthesis of water dispersible boron core silica shell (B@SiO2) nanoparticles
NASA Astrophysics Data System (ADS)
Walton, Nathan I.; Gao, Zhe; Eygeris, Yulia; Ghandehari, Hamidreza; Zharov, Ilya
2018-04-01
Water dispersible boron nanoparticles have great potential as materials for boron neutron capture therapy of cancer and magnetic resonance imaging, if they are prepared on a large scale with uniform size and shape and hydrophilic modifiable surface. We report the first method to prepare spherical, monodisperse, water dispersible boron core silica shell nanoparticles (B@SiO2 NPs) suitable for aforementioned biomedical applications. In this method, 40 nm elemental boron nanoparticles, easily prepared by mechanical milling and carrying 10-undecenoic acid surface ligands, are hydrosilylated using triethoxysilane, followed by base-catalyzed hydrolysis of tetraethoxysilane, which forms a 10-nm silica shell around the boron core. This simple two-step process converts irregularly shaped hydrophobic boron particles into the spherically shaped uniform nanoparticles. The B@SiO2 NPs are dispersible in water and the silica shell surface can be modified with primary amines that allow for the attachment of a fluorophore and, potentially, of targeting moieties. [Figure not available: see fulltext.
Synthesis of Cross-Linked Polymeric Micelle pH Nanosensors: An Investigation of Design Flexibility.
Kumar, E K Pramod; Jølck, Rasmus I; Andresen, Thomas L
2015-09-01
The design flexibility that polymeric micelles offer in the fabrication of optical nanosensors for ratiometric pH measurements is investigated. pH nanosensors based on polymeric micelles are synthesized either by a mixed-micellization approach or by a postmicelle modification strategy. In the mixed-micellization approach, self-assembly of functionalized unimers followed by shell cross-linking by copper-catalyzed azide-alkyne cycloaddition (CuAAC) results in stabilized cRGD-functionalized micelle pH nanosensors. In the postmicelle modification strategy, simultaneous cross-linking and fluorophore conjugation at the micelle shell using CuAAC results in a stabilized micelle pH nanosensor. Compared to the postmicelle modification strategy, the mixed-micellization approach increases the control of the overall composition of the nanosensors. Both approaches provide stable nanosensors with similar pKa profiles and thereby nanosensors with similar pH sensitivity. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Khodadadi, Bahar; Bordbar, Maryam; Nasrollahzadeh, Mahmoud
2017-05-01
In this paper, silver nanoparticles (Ag NPs) are synthesized using Achillea millefolium L. extract as reducing and stabilizing agents and peach kernel shell as an environmentally benign support. FT-IR spectroscopy, UV-Vis spectroscopy, X-ray Diffraction (XRD), Field emission scanning electron microscopy (FESEM), Energy Dispersive X-ray Spectroscopy (EDS), Thermo gravimetric-differential thermal analysis (TG-DTA) and Transmission Electron Microscopy (TEM) were used to characterize peach kernel shell, Ag NPs, and Ag NPs/peach kernel shell. The catalytic activity of the Ag NPs/peach kernel shell was investigated for the reduction of 4-nitrophenol (4-NP), Methyl Orange (MO), and Methylene Blue (MB) at room temperature. Ag NPs/peach kernel shell was found to be a highly active catalyst. In addition, Ag NPs/peach kernel shell can be recovered and reused several times with no significant loss of its catalytic activity. Copyright © 2017 Elsevier Inc. All rights reserved.
Biodegradable chitosan nanogels crosslinked with genipin.
Arteche Pujana, Maite; Pérez-Álvarez, Leyre; Cesteros Iturbe, Luis Carlos; Katime, Issa
2013-05-15
Chitosan nanoparticles crosslinked with genipin were prepared by reverse microemulsion that allowed to obtain highly monodisperse (3-20 nm by TEM) nanogels. The incorporation of genipin into chitosan was confirmed and quantitatively evaluated by UV-vis and (1)H NMR. Loosely crosslinked chitosan networks showed higher water solubility at neutral pHs than pure chitosan. The hydrodynamic diameter of the genipin-chitosan nanogels ranged from 270 to 390 nm and no remarkable differences were found when the crosslinking degree was varied. The hydrodynamic diameters of the nanoparticles increased slightly at acidic pH and the protonation of ionizable amino groups with the pH was confirmed by the zeta potential measurements. The biocompatible and biodegradable nature, as well as the colloidal and monodisperse particle size of the prepared nanogels, make them attractive candidates for a large variety of biomedical applications. Copyright © 2013 Elsevier Ltd. All rights reserved.
Williams, George M [Portland, OR; Schut, David M [Philomath, OR; Stonas, Andreas [Albany, OR
2011-08-09
A photovoltaic device has nanoparticles sandwiched between a conductive substrate and a charge selective transport layer. Each of the nanoparticles has a ligand shell attached to the nanoparticle core. A first type of ligand is electron rich and attached to one hemisphere of the nanoparticle core, while a second type of ligand is electron poor and attached to an opposite hemisphere of the core. Consequently, the ligand shell induces an electric field within the nanoparticle, enhancing the photovoltaic effect. The arrangement of ligands types on different sides of the nanoparticle is obtained by a process involving ligand substitution after adhering the nanoparticles to the conductive substrate.
Coercivity and Exchange Bias Study of Polycrystalline Hollow Nanoparticles
NASA Astrophysics Data System (ADS)
Bah, Mohamed Alpha
Magnetic nanoparticles (NPs) have the potential to be useful in a variety of applications such as biomedical instruments, catalysis, sensing, recording information, etc. These nanoparticles exhibit remarkably different properties compared to their bulk counter parts. Synthesis of magnetic NPs with the right morphology, phase, size and surface functionality, as well as their usage for specific applications are challenging in terms of efficiency and safety. Morphology wise, there have been numerous reports on magnetic nanoparticles where morphologies such as core/shell, hollow, solid, etc., have been explored. It has been shown that morphology affects the magnetic response. Achieving the right crystal structure with required morphology and the magnetic behavior of the nanoparticle phases determines the magnetic response of the structure. For example, in the case of core/shell NPs various ferromagnetic (FM), ferrimagnetic (FiM), and antiferromagnetic (AFM) core and shell combinations have been reported. In these cases, interesting and strikingly different features, such as unusually high spin glass transition temperature, large exchange bias, finite size effects, magnetic proximity effects, unusual trend of blocking temperature as function of average crystal size, etc., have been reported. More specifically, the morphology of core/shell nanoparticles provides added degrees of freedom compared to conventional solid magnetic nanoparticles, including variations in the size, phase and material of the core and shell of the particle, etc. which helps enhance their magnetic properties. Similar to traditional core/shell nanoparticles, inverted core/shell having a FiM or FM order above the Curie temperature (TC) of the shell has been reported where the Neel temperature (TN) is comparable with the bulk value and there is nonmonotonic dependence of the coercive field (HC) and exchange bias (HEB) on the core diameter. In addition to the core/shell morphology, nanoparticles with hollow morphology are also of interest to the scientific community. For such cases, surface spin glass transition enhancements have been reported due to the presence of the additional inner surface. CoFe2O4, NiFe 2O4 and gamma-Fe2O3 hollow nanoparticles exhibit strikingly contrasting magnetic behavior compared to bulk and conventional solid particles; similar behavior was also observed in core/shell nanoparticles. Structurally, hollow polycrystalline nanoparticles are composed of multiple crystallographic domains. This random orientation of the crystallographic domains also causes randomization of the local anisotropy axes. Hence the overall effect of this morphology on the magnetic properties is exhibited through the high coercivity, relatively high temperature magnetic irreversibility, lack of magnetic saturation, high blocking temperature, etc. Over the years, extensive work on core/shell nanoparticles have been carried out to understand their exchange bias phenomenon and the effect on coercivity. Recently, focus has been given to hollow polycrystalline nanoparticles for the reason mentioned above. This thesis investigates the root cause for the above-mentioned effects on the coercivity and exchange bias. Since hollow nanoparticles with polycrystalline structure have shown to exhibit different and improved magnetic behavior compared to bulk and other conventional solid particles, they will be the focus of our investigation. First, extensive field and temperature dependent magnetic study on polycrystalline hollow nickel ferrite (NiFe2O4) have revealed the effect of the presence of inner surface in a single oxide nanoparticle. Second, the effect of having multiple oxides with different magnetic properties (i.e. FM and AFM) in a single nanoparticle, while maintaining a hollow morphology was investigated by studying polycrystalline hollow gamma-Mn2O3 and MnO nanoparticles. Studies on various conventional solid manganese oxide nanoparticles have already been reported. Therefore, focus was only made on the fabrication and magnetic study of hollow polycrystalline manganese oxide, with a comparison of the results to those from solid nanoparticles already available in literature. A conclusion was drawn to the importance of the coupling of different magnetic phases (i.e. FM and AFM, FiM and AFM, or SG and AFM), in contrast to just having one single oxide in the hollow nanoparticles. Finally, the importance of this coupling as compared to the increase of surface-to-volume ratio was evaluated in CoO/Co3O4/CoFe2O4 polycrystalline hollow nanoparticles by varying the AFM phase (CoO/Co 3O4) in the nanoparticles and observing how the magnetic properties varied. This system helped address the effect of the coupling between different magnetic phases, super-exchange interaction, and proximity effect.
Development of drug-loaded chitosan-vanillin nanoparticles and its cytotoxicity against HT-29 cells.
Li, Pu-Wang; Wang, Guang; Yang, Zi-Ming; Duan, Wei; Peng, Zheng; Kong, Ling-Xue; Wang, Qing-Huang
2016-01-01
Chitosan as a natural polysaccharide derived from chitin of arthropods like shrimp and crab, attracts much interest due to its inherent properties, especially for application in biomedical materials. Presently, biodegradable and biocompatible chitosan nanoparticles are attractive for drug delivery. However, some physicochemical characteristics of chitosan nanoparticles still need to be further improved in practice. In this work, chitosan nanoparticles were produced by crosslinking chitosan with 3-methoxy-4-hydroxybenzaldehyde (vanillin) through a Schiff reaction. Chitosan nanoparticles were 200-250 nm in diameter with smooth surface and were negatively charged with a zeta potential of - 17.4 mV in neutral solution. Efficient drug loading and drug encapsulation were achieved using 5-fluorouracil as a model of hydrophilic drug. Drug release from the nanoparticles was constant and controllable. The in vitro cytotoxicity against HT-29 cells and cellular uptake of the chitosan nanoparticles were evaluated by methyl thiazolyl tetrazolium method, confocal laser scanning microscope and flow cytometer, respectively. The results indicate that the chitosan nanoparticles crosslinked with vanillin are a promising vehicle for the delivery of anticancer drugs.
NASA Astrophysics Data System (ADS)
Skaat, Hadas; Belfort, Georges; Margel, Shlomo
2009-06-01
Maghemite (γ-Fe2O3) magnetic nanoparticles of 15.0 ± 2.1 nm are formed by nucleation followed by controlled growth of maghemite thin films on gelatin-iron oxide nuclei. Uniform magnetic γ-Fe2O3/poly (2,2,3,3,4,4,4-heptafluorobutyl acrylate) (γ-Fe2O3/PHFBA) core-shell nanoparticles are prepared by emulsion polymerization of the fluorinated monomer 2,2,3,3,4,4,4-heptafluorobutyl acrylate (HFBA) in the presence of the maghemite nanoparticles. The kinetics of the insulin fibrillation process in the absence and in the presence of the γ-Fe2O3/PHFBA core-shell nanoparticles are elucidated. A significant direct slow transition from α-helix to β-sheets during insulin fibril formation is observed in the presence of the γ-Fe2O3/PHFBA nanoparticles. This is in contradiction to our previous manuscript, which illustrated that the γ-Fe2O3 core nanoparticles do not affect the kinetics of the formation of the insulin fibrils, and to other previous publications that describe acceleration of the fibrillation process by using various types of nanoparticles. These core-shell nanoparticles may therefore be also useful for the inhibition of conformational changes of other amyloidogenic proteins that lead to neurodegenerative diseases such as Alzheimer's, Parkinson's, Huntington's, mad cow and prion diseases.
NASA Astrophysics Data System (ADS)
Verma, Jaya; Nigam, Subhasha; Sinha, Surbhi; Sikarwar, B. S.; Bhattacharya, Arpita
2017-12-01
Irradiation effect of low-energy ion beam has been investigated on nanocoating developed with silica, titania and silica-titania core-shell nanoparticles embedded in an organic binder for nanopaint application. In this work, we have taken polyurethane as a model organic binder. Silica nanoparticles have been prepared through sol-gel synthesis with a particle size of 85 nm. Titania and core-shell nanoparticles have been prepared through both sol-gel and peptization process. Particle sizes obtained were 107 nm for titania and 240 nm for core-shell nanoparticles prepared through sol-gel process and 75 nm for TiO2 and 144 nm for core-shell nanoparticles prepared through peptization process. The coating formulations were developed with the above nanoparticles individually and nanoparticle concentration was varied from 1 to 6 wt% and the best performance in terms of hydrophobicity was obtained with 4 wt % of the nanoparticles in polyurethane coating formulation. All the coating formulations prepared were applied on a glass substrate and dried at 100°C. The dry film thickness obtained was around 100 µm in each case. These films dried on glass substrate were irradiated by nitrogen and argon ion beam with energy of 26 keV at fluences of 1014 to 1016 ions/cm2. The anti-algal property of the irradiated samples was improved and hydrophobicity was reduced.
Tunable poly(methacrylic acid-co-acrylamide) nanoparticles through inverse emulsion polymerization.
Zhong, Justin X; Clegg, John R; Ander, Eric W; Peppas, Nicholas A
2018-06-01
Environmentally responsive biomaterials have played key roles in the design of biosensors and drug delivery vehicles. Their physical response to external stimuli, such as temperature or pH, can transduce a signal or trigger the release of a drug. In this work, we designed a robust, highly tunable, pH-responsive nanoscale hydrogel system. We present the design and characterization of poly(methacrylic acid-co-acrylamide) hydrogel nanoparticles, crosslinked with methylenebisacrylamide, through inverse emulsion polymerization. The effects of polymerization parameters (i.e., identities and concentrations of monomer and surfactant) and polymer composition (i.e., weight fraction of ionic and crosslinking monomers) on the nanoparticles' bulk and environmentally responsive properties were determined. We generated uniform, spherical nanoparticles which, through modulation of crosslinking, exhibit a volume swelling of 1.77-4.07, relative to the collapsed state in an acidic environment. We believe our system has potential as a base platform for the targeted, injectable delivery of hydrophilic therapeutics. With equal importance, however, we hope that our systematic analysis of the individual impacts of polymerization and purification conditions on nanoparticle composition, morphology, and performance can be used to expedite the development of alternate hydrophilic nanomaterials for a range of biomedical applications. © 2018 Wiley Periodicals, Inc. J Biomed Mater Res Part A: 106A: 1677-1686, 2018. © 2018 Wiley Periodicals, Inc.
NASA Astrophysics Data System (ADS)
Tian, Suyun; Zhu, Guannan; Tang, Yanping; Xie, Xiaohua; Wang, Qian; Ma, Yufei; Ding, Guqiao; Xie, Xiaoming
2018-03-01
Various graphene-based Si nanocomposites have been reported to improve the performance of active materials in Li-ion batteries. However, these candidates still yield severe capacity fading due to the electrical disconnection and fractures caused by the huge volume changes over extended cycles. Therefore, we have designed a novel three-dimensional cross-linked graphene and single-wall carbon nanotube structure to encapsulate the Si nanoparticles. The synthesized three-dimensional structure is attributed to the excellent self-assembly of carbon nanotubes with graphene oxide as well as a thermal treatment process at 900 °C. This special structure provides sufficient void spaces for the volume expansion of Si nanoparticles and channels for the diffusion of ions and electrons. In addition, the cross-linking of the graphene and single-wall carbon nanotubes also strengthens the stability of the structure. As a result, the volume expansion of the Si nanoparticles is restrained. The specific capacity remains at 1450 mAh g-1 after 100 cycles at 200 mA g-1. This well-defined three-dimensional structure facilitates superior capacity and cycling stability in comparison with bare Si and a mechanically mixed composite electrode of graphene, single-wall carbon nanotubes and silicon nanoparticles.
Weaver, John B; Rauwerdink, Kristen M; Rauwerdink, Adam M; Perreard, Irina M
2013-12-01
The rigidity of the extracellular matrix and of the integrin links to the cytoskeleton regulates signaling cascades, controlling critical aspects of cancer progression including metastasis and angiogenesis. We demonstrate that the matrix stiffness can be monitored using magnetic spectroscopy of nanoparticle Brownian motion (MSB). We measured the MSB signal from nanoparticles bound to large dextran polymers. The number of glutaraldehyde induced cross-links was used as a surrogate for material stiffness. There was a highly statistically significant change in the MSB signal with the number of cross-links especially prominent at higher frequencies. The p-values were all highly significant. We conclude that the MSB signal can be used to identify and monitor changes in the stiffness of the local matrix to which the nanoparticles are bound.
Investigation of novel inverted NiO@NixCo1-xO core-shell nanoparticles
NASA Astrophysics Data System (ADS)
Hasan, Samiul; Mayanovic, R. A.; Benamara, Mourad
2018-05-01
Inverse core-shell nanoparticles, comprised of an antiferromagnetic (AFM) core covered by a ferromagnetic (FM) or ferrimagnetic (FiM) shell, are of current interest due to their different potential application and due to the tunability of their magnetic properties. The antiferromagnetic nature of NiO and high Néel temperature (523 K) makes this material well suited for inverse core-shell nanoparticle applications. Our primary objective in this project has been to synthesize and characterize inverted core-shell nanoparticles (CSNs) comprised of a NiO (AFM) core and a shell consisting of a NixCo1-xO (FiM) compound. The synthesis of the CSNs was made using a two-step process. The NiO nanoparticles were synthesized using a chemical reaction method. Subsequently, the NiO nanoparticles were used to grow the NiO@NixCo1-xO CSNs using our hydrothermal nano-phase epitaxy method. XRD structural characterization shows that the NiO@NixCo1-xO CSNs have the rock salt cubic crystal structure. SEM-EDS data indicates the presence of Co in the CSNs. Magnetic measurements show that the CSNs exhibit AFM/FiM characteristics with a small coercivity field of 30 Oe at 5 K. The field cooled vs zero field cooled hysteresis loop measurements show a magnetization axis shift which is attributed to the exchange bias effect between the AFM NiO core and an FiM NixCo1-xO shell of the CSNs. Our ab initio based calculations of the NixCo1-xO rock salt structure confirm a weak FiM character and a charge transfer insulator property of the compound.
NASA Astrophysics Data System (ADS)
Liu, Lian; Yang, Pengfei; Li, Junying; Zhang, Zhiliang; Yu, Xi; Lu, Ling
2017-05-01
Sliver nanoparticles (AgNPs) were synthesized and functionalized with furan group on their surface, followed by the reverse Diels-Alder (DA) reaction with bismaleimide to vary the particle size, so as to give different antibacterial activities. These nanoparticles were characterized using Scanning Electron Microscope (SEM), X-Ray Diffraction (XRD), Ultraviolet-Visible (UV-vis), Nanoparticle Size Analyzer and X-Ray Photoelectron Spectroscopy (XPS). It was found that the cross-linking reaction with bismaleimide had a great effect on the size of AgNPs. The size of the AgNPs could be controlled by the temperature of DA/r-DA equilibrium. The antibacterial activity was assessed using the inhibition zone diameter by introducing the particles into a media containing Escherichia coli, Listeria monocytogenes, and Staphylococcus aureus, respectively. It was found that these particles were effective bactericides. Furthermore, the antibacterial activity of the nanoparticles decreased orderly as the particle size enlarged.
The tracer diffusion coefficient of soft nanoparticles in a linear polymer matrix
Imel, Adam E.; Rostom, Sahar; Holley, Wade; ...
2017-03-09
The diffusion properties of nanoparticles in polymer nanocomposites are largely unknown and are often difficult to determine experimentally. To address this shortcoming, we have developed a novel method to determine the tracer diffusion coefficient of soft polystyrene nanoparticles in a linear polystyrene matrix. Monitoring the interdiffusion of soft nanoparticles into a linear polystyrene matrix provides the mutual diffusion coefficient of this system, from which the tracer diffusion coefficient of the soft nanoparticle can be determined using the slow mode theory. Utilizing this protocol, the role of nanoparticle molecular weight and rigidity on its tracer diffusion coefficient is provided. These resultsmore » demonstrate that the diffusive behavior of these soft nanoparticles differ from that of star polymers, which is surprising since our recent studies suggest that the nanoparticle interacts with a linear polymer similarly to that of a star polymer. It appears that these deformable nanoparticles mostly closely mimic the diffusive behavior of fractal macromolecular architectures or microgels, where the transport of the nanoparticle relies on the cooperative motion of neighboring linear chains. Finally, the less cross-linked, and thus more deformable, nanoparticles diffuse faster than the more highly crosslinked nanoparticles, presumably because the increased deformability allows the nanoparticle to distort and fit into available space.« less
NASA Astrophysics Data System (ADS)
Tadyszak, Krzysztof; Kertmen, Ahmet; Coy, Emerson; Andruszkiewicz, Ryszard; Milewski, Sławomir; Kardava, Irakli; Scheibe, Błażej; Jurga, Stefan; Chybczyńska, Katarzyna
2017-07-01
Superparamagnetic behavior in aqueously well dispersible magnetite core-shell Fe3O4@SiO2 nanoparticles is presented. The magnetic properties of core-shell nanoparticles were measured with use of the DC, AC magnetometry and EPR spectroscopy. Particles where characterized by HR-TEM and Raman spectroscopy, showing a crystalline magnetic core of 11.5 ± 0.12 nm and an amorphous silica shell of 22 ± 1.5 nm in thickness. The DC, AC magnetic measurements confirmed the superparamagnetic nature of nanoparticles, additionally the EPR studies performed at much higher frequency than DC, AC magnetometry (9 GHz) have confirmed the paramagnetic nature of the nanoparticles. Our results show the excellent magnetic behavior of the particles with a clear magnetite structure, which are desirable properties for environmental remediation and biomedical applications.
The Effect of Ligands on FePt–Fe 3O 4 Core–Shell Magnetic Nanoparticles
Kim, Dong-Hyun; Tamada, Yoshinori; Ono, Teruo; ...
2014-03-01
FePt–Fe 3O 4 core–shell nanoparticles functionalized with 3,4-dihydroxyphenylacetic acid (DOPAC) and dimercaptosuccinic acid (DMSA) ligands were synthesized and characterized. We also found that the DOPAC ligand enhances the magnetic properties of the FePt–Fe 3O 4 particles, in comparison with the DMSA ligand, which induces the oxidation of the shell layer that causes a significant reduction of the saturation magnetization. We evaluated the synthesized magnetic nanoparticles for applications in magnetic hyperthermia and magnetic resonance imaging contrast enhancement.
NASA Astrophysics Data System (ADS)
Siegwart, Daniel John
In this thesis, atom transfer radical polymerization (ATRP) and reversible addition-fragmentation chain transfer (RAFT) polymerization were utilized in the design of synthetic polymers to create tissue engineering scaffolds and drug delivery systems with improved control over structure and functionality. Thermo-sensitive injectable hydrogels based on poly(NIPAAm) with degradable ester units within the polymer backbone and at the cross-linking sites were prepared using ATRP and RAFT. Solvent induced morphologies of poly(methyl methacrylate-b-ethylene oxide-b-methyl methacrylate) triblock copolymers synthesized by ATRP were described. A micellar structure, composed of a hydrophobic PMMA core and a PEO shell was constructed for delivery of hydrophobic drugs. ATRP was carried out in inverse miniemulsion to prepare well defined functional nanogels that were capable of entrapping and releasing various molecules (Doxorubicin, carbohydrate-based drugs, fluorophores, and gold nanoparticles). The results demonstrated that nanogels prepared by ATRP in inverse miniemulsion could be internalized into cells via clathrin-mediated endocytosis. Nanogels functionalized with integrin-binding peptides increased cellular uptake. A process called Atom Transfer Radical Coupling (ATRC) was also described, which illustrated the power of functionality in ATRP. Finally, linear polymers and cross-linked nanogels were synthesized by ATRP and functionalized with biotin, pyrene, and peptide sequences, tying together the overall themes of structural control and functionality.
Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia
NASA Astrophysics Data System (ADS)
Robles, J.; Das, R.; Glassell, M.; Phan, M. H.; Srikanth, H.
2018-05-01
We report a systematic study of the effects of core and shell size on the magnetic properties and heating efficiency of exchange-coupled Fe3O4/CoFe2O4 core/shell nanoparticles. The nanoparticles were synthesized using thermal decomposition of organometallic precursors. Transmission electron microscopy (TEM) confirmed the formation of spherical Fe3O4 and Fe3O4/CoFe2O4 nanoparticles. Magnetic measurements showed high saturation magnetization for the nanoparticles at room temperature. Increasing core diameter (6.4±0.7, 7.8±0.1, 9.6±1.2 nm) and/or shell thickness (˜1, 2, 4 nm) increased the coercive field (HC), while an optimal value of saturation magnetization (MS) was achieved for the Fe3O4 (7.8±0.1nm)/CoFe2O4 (2.1±0.1nm) nanoparticles. Magnetic hyperthermia measurements indicated a large increase in specific absorption rate (SAR) for 8.2±1.1 nm Fe3O4/CoFe2O4 compared to Fe3O4 nanoparticles of same size. The SAR of the Fe3O4/CoFe2O4 nanoparticles increased from 199 to 461 W/g for 800 Oe as the thickness of the CoFe2O4 shell was increased from 0.9±0.5 to 2.1±0.1 nm. The SAR enhancement is attributed to a combination of the large MS and the large HC. Therefore, these Fe3O4/CoFe2O4 core/shell nanoparticles can be a good candidate for advanced hyperthermia application.
Exchange-coupled Fe3O4/CoFe2O4 nanoparticles for advanced magnetic hyperthermia
NASA Astrophysics Data System (ADS)
Glassell, M.; Robles, J.; Das, R.; Phan, M. H.; Srikanth, H.
Iron oxide nanoparticles especially Fe3O4, γ-Fe2O3 have been extensively studied for magnetic hyperthermia because of their tunable magnetic properties and stable suspension in superparamagnetic regime. However, their relatively low heating capacity hindered practical application. Recently, a large improvement in heating efficiency has been reported in exchange-coupled nanoparticles with exchange coupling between soft and hard magnetic phases. Here, we systematically studied the effect of core and shell size on the heating efficiency of the Fe3O4/CoFe2O4 core/shell nanoparticles. The nanoparticles were synthesized using thermal decomposition of organometallic precursors. Transmission electron microscopy (TEM) showed formation of spherical shaped Fe3O4 and Fe3O-/CoFe2O4 nanoparticles. Magnetic measurements showed high magnetization (≅70 emu/g) and superparamagnetic behavior for the nanoparticles at room temperature. Magnetic hyperthermia results showed a large increase in specific absorption rate (SAR) for 8nm Fe3O4/CoFe2O4 compared to Fe3O4 nanoparticles of the same size. The heating efficiency of the Fe3O4/CoFe2O4 with 1 nm CoFe2O4 (shell) increased from 207 to 220 W/g (for 800 Oe) with increase in core size from 6 to 8 nm. The heating efficiency of the Fe3O4/CoFe2O4 with 2 nm CoFe2O4 (shell) and core size of 8 nm increased from 220 to 460 W/g (for 800 Oe). These exchange-coupled Fe3O4/CoFe2O4 core/shell nanoparticles can be a good candidate for advanced hyperthermia application.
SYNTHESIS AND APPLICATIONS OF Fe3O4/SiO2 CORE-SHELL MATERIALS.
Sonmez, Maria; Georgescu, Mihai; Alexandrescu, Laurentia; Gurau, Dana; Ficai, Anton; Ficai, Denisa; Andronescu, Ecaterina
2015-01-01
Multifunctional nanoparticles based on magnetite/silica core-shell, consisting of iron oxides coated with silica matrix doped with fluorescent components such as organic dyes (fluorescein isothiocyanate - FITC, Rhodamine 6G) or quantum dots, have drawn remarkable attention in the last years. Due to the bi-functionality of these types of nanoparticles (simultaneously having magnetic and fluorescent properties), they are successfully used in highly efficient human stem cell labeling, magnetic carrier for photodynamic therapy, drug delivery, hyperthermia and other biomedical applications. Another application of core-shell-based nanoparticles, in which the silica is functionalized with aminosilanes, is for immobilization and separation of various biological entities such as proteins, antibodies, enzymes etc. as well as in environmental applications, as adsorbents for heavy metal ions. In vitro tests on human cancerous cells, such as A549 (human lung carcinoma), breast, human cervical cancer, THP-1 (human acute monocytic leukaemia) etc. , were conducted to assess the potential cytotoxic effects that may occur upon contact of nanoparticles with cancerous tissue. Results show that core-shell nanoparticles doped with cytostatics (cisplatin, doxorubicin, etc.), are easily adsorbed by affected tissue and in some cases lead to an inhibition of cell proliferation and induce cell death by apoptosis. The goal of this review is to summarize the advances in the field of core-shell materials, particularly those based on magnetite/silica with applicability in medicine and environmental protection. This paper briefly describes synthesis methods of silica-coated magnetite nanoparticles (Stöber method and microemulsion), the method of encapsulating functional groups based on aminosilanes in silica shell, as well as applications in medicine of these types of simple or modified nanoparticles for cancer therapy, MRI, biomarker immobilization, drug delivery, biocatalysis etc., and in environmental applications (removal of heavy metal ions and catalysis).
An, Wei; Liu, Ping
2015-09-18
Improving the activity and stability of Pt-based core–shell nanocatalysts for proton exchange membrane fuel cells while lowering Pt loading has been one of the big challenges in electrocatalysis. Here, using density functional theory, we report the effect of adding Au as the third element to enhance the durability and activity of Ni@Pt core–shell nanoparticles (NPs) during the oxygen reduction reaction (ORR). Our results show that the durability and activity of a Ni@Pt NP can be finely tuned by controlling Au concentration and distribution. For a NiAu@Pt NP, the durability can be greatly promoted by thermodynamically favorable segregation of Au tomore » replace the Pt atoms at vertex, edge, and (100) facets on the shell, while still keeping the ORR activity on the active Pt(111) shell as high as that of Ni@Pt nanoparticles. Such behavior strongly depends on a direct interaction with the Ni interlayer. The results not only highlight the importance of interplay between surface strain on the shell and the interlayer–shell interaction in determining the durability and activity but also provide guidance on how to maximize the usage of Au to optimize the performance of core–shell (Pt) nanoparticles. As a result, such understanding has allowed us to discover a novel NiAu@Pt nanocatalyst for the ORR.« less
NASA Astrophysics Data System (ADS)
Fadhilah, Nur; Alhadi, Emha Riyadhul Jinan; Risanti, Doty Dewi
2018-04-01
The Au nanoparticles as core can increase the light harvesting due to the strong near-field effect LSPR (Localized Surface Plasmon Resonance), effectively minimized the electron recombination process and also can improve the optical absorption of the dye sensitized. Au@SiO2 core-shell nanoparticles were prepared using SiO2 extracted from Sidoarjo mud volcano. In this work investigated the influence of pH solution and silica shell volume fraction in Au@SiO2 nanoparticles core-shell structure on DSSC loaded with Ru-based dye. From XRD characterization it was found that core-shell contains SiO2, Au, γAl2O3 and traces NaCl. UV-Vis absorption spectra of core-shell showed the position of the surface plasmon AuNP band in the range of 500-600 nm. The Au@SiO2 core-shell with volume fraction of 30ml silica has the highest peak absorbance. The enhanced light absorption is primarily attributed to the LSPR effect of the Au core. Our results on incident photon-to-current conversion efficiency indicates that the presence of SiO2 depending on its volume fraction tends to shift to longer wavelength.
Enhanced stability of Janus nanoparticles by covalent cross-linking of surface ligands.
Song, Yang; Klivansky, Liana M; Liu, Yi; Chen, Shaowei
2011-12-06
A mercapto derivative of diacetylene was used as the hydrophilic ligand to prepare Janus nanoparticles by using hydrophobic hexanethiolate-protected gold (AuC6, diameter 5 nm) nanoparticles as the starting materials. The amphiphilic surface characters of the Janus nanoparticles were verified by contact angle measurements, as compared to those of the bulk-exchange counterparts where the two types of ligands were distributed rather homogeneously on the nanoparticle surface. Dynamic light scattering studies showed that the Janus nanoparticles formed stable superstructures in various solvent media that were significantly larger than those by the bulk-exchange counterparts. This was ascribed to the amphiphilic characters of the Janus nanoparticles that rendered the particles to behave analogously to conventional surfactant molecules. Notably, because of the close proximity of the diacetylene moieties on the Janus nanoparticle surface, exposure to UV irradiation led to effective covalent cross-linking between the diacetylene moieties of neighboring ligands, as manifested in UV-vis and fluorescence measurements where the emission characteristics of dimers and trimers of diacetylene were rather well-defined, in addition to the monomeric emission. In contrast, for bulk-exchange nanoparticles, no trimer emission could be identified, and the intensity of dimer emission was markedly lower (though the intensity increased with increasing diacetylene coverage on the particle surface) under the otherwise identical experimental conditions. This is largely because the diacetylene ligands were distributed on the entire particle surface, and it was difficult to find a large number of ligands situated closely so that the stringent topochemical principles for the polymerization of diacetylene derivatives could be met. Importantly, the cross-linked Janus nanoparticles were found to exhibit marked enhancement of the structural integrity, which was attributable to the impeded surface diffusion of the thiol ligands on the nanoparticle surface, as manifested in fluorescence measurements of aged nanoparticles. © 2011 American Chemical Society
Rudolph, Tobias; Barthel, Markus J; Kretschmer, Florian; Mansfeld, Ulrich; Hoeppener, Stephanie; Hager, Martin D; Schubert, Ulrich S; Schacher, Felix H
2014-05-01
Furfuryl glycidyl ether (FGE) represents a highly versatile monomer for the preparation of reversibly cross-linkable nanostructured materials via Diels-Alder reactions. Here, the use of FGE for the mid-chain functionalization of a P2VP-b-PEO diblock copolymer is reported. The material features one furan moiety at the block junction, P2VP68 -FGE-b-PEO390 , which can be subsequently addressed in Diels-Alder reactions using maleimide-functionalized counterparts. The presence of the FGE moiety enables the introduction of dyes as model labels or the formation of hetero-grafted brushes as shell on hybrid Au@Polymer nanoparticles. This renders P2VP68 -FGE-b-PEO390 , a powerful tool for selective functionalization reactions, including the modification of surfaces. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Khan, Huda; Shukla, R N; Bajpai, A K
2016-04-01
The aim of the present investigation was to design biocompatible gelatin nanoparticles, capable of releasing the cytarabine drug in a controllable way by regulating the extent of swelling of nanoparticles. In order to achieve the proposed objectives, gelatin (Type A, derived from acid cured tissue) was modified by crosslinking with genipin and nanoparticles of crosslinked gelatin were prepared using single water in oil (W/O) emulsion technique. The nanoparticles were characterized by techniques like FTIR, SEM, TEM, particles size analysis, and surface potential measurements. The nanoparticle chemical architecture was found to influence drug-releasing capacity. The influence of experimental conditions such as pH and simulated physiological fluids as the release medium was also investigated on the release profiles of cytarabine. It is possible to fabricate high-performance materials, by designing of controlled size gelatin nanoparticles with good biocompatible properties along with desired drug release profiles. Copyright © 2015 Elsevier B.V. All rights reserved.
O’Brien, Victor; Chang, Andrew; Blanco, Matthew; Zabalegui, Aitor; Lee, Hohyun; Asuri, Prashanth
2015-01-01
Current studies investigating properties of nanoparticle-reinforced polymers have shown that nanocomposites often exhibit improved properties compared to neat polymers. However, over two decades of research, using both experimental studies and modeling analyses, has not fully elucidated the mechanistic underpinnings behind these enhancements. Moreover, few studies have focused on developing an understanding among two or more polymer properties affected by incorporation of nanomaterials. In our study, we investigated the elastic and thermal properties of poly(acrylamide) hydrogels containing silica nanoparticles. Both nanoparticle concentration and size affected hydrogel properties, with similar trends in enhancements observed for elastic modulus and thermal diffusivity. We also observed significantly lower swellability for hydrogel nanocomposites relative to neat hydrogels, consistent with previous work suggesting that nanoparticles can mediate pseudo crosslinking within polymer networks. Collectively, these results indicate the ability to develop next-generation composite materials with enhanced mechanical and thermal properties by increasing the average crosslinking density using nanoparticles. PMID:26301505
NASA Astrophysics Data System (ADS)
S, Abdul Khalil H. P.; Masri, M.; Saurabh, Chaturbhuj K.; Fazita, M. R. N.; Azniwati, A. A.; Sri Aprilia, N. A.; Rosamah, E.; Dungani, Rudi
2017-03-01
In the present study, a successful attempt has been made on enhancing the properties of hybrid kenaf/coconut fibers reinforced vinyl ester composites by incorporating nanofillers obtained from coconut shell. Coconut shells were grinded followed by 30 h of high energy ball milling for the production of nanoparticles. Particle size analyzer demonstrated that the size of 90% of obtained nanoparticles ranged between 15-140 nm. Furthermore, it was observed that the incorporation of coconut shell nanofillers into hybrid composite increased water absorption capacity. Moreover, tensile, flexural, and impact strength increased with the filler loading up to 3 wt.% and thereafter decrease was observed at higher filler concentration. However, elongation at break decreased and thermal stability increased in nanoparticles concentration dependent manner. Morphological analysis of composite with 3% of filler loading showed minimum voids and fiber pull outs and this indicated that the stress was successfully absorbed by the fiber.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Sun, Yu-Gang; Truong, Tu T.; Liu, Yu-Zi
2015-02-01
Microflowers made of interconnected MnO2 nanosheets have been successfully synthesized in a microwave reactor through a hydrothermal reduction of KMnO4 with aqueous HCl at elevated temperatures in the presence of superparamagnetic Fe3O4@SiO2 core-shell nanoparticles. Due to the chemical compatibility between SiO2 and MnO2, the heterogeneous reaction leads to the spontaneous encapsulation of the Fe3O4@SiO2 core-shell nanoparticles in the MnO2 microflowers. The resulting hybrid particles exhibit multiple properties including high surface area associated with the MnO2 nanosheets and superparamagnetism originated from the Fe3O4@SiO2 core-shell nanoparticles, which are beneficial for applications requiring both high surface area and magnetic separation. (C) 2014 Yu-Gangmore » Sun.« less
Allouche, Joachim; Dupin, Jean-Charles; Gonbeau, Danielle
2011-07-14
Silica core-shell nanoparticles with a MSU shell have been synthesized using several non-ionic poly(ethylene oxide) based surfactants via a two step sol-gel method. The materials exhibit a typical worm-hole pore structure and tunable pore diameters between 2.4 nm and 5.8 nm.
A facile synthesis based on the addition of ascorbic acid to a mixture of Na2PdCl4, K2PtCl6, and Pluronic P123 results in highly branched core–shell nanoparticles (NPs) with a micro–mesoporous dandelion-like morphology comprising Pd core and Pt shell. The slow reduction kinetics ...
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chang Lianxia; Yang Haibin; Fu Wuyou
W/WS{sub 2} inorganic fullerene-like (IF) nanoparticles with core-shell structure are synthesized by the reaction of tungsten nanospheres and sulfur at relatively low temperatures (380-600 deg. C) under hydrogen atmosphere, in which tungsten nanospheres were prepared by wire electrical explosion method. Images of transmission electron microscopy and high-resolution transmission electron microscopy show that the composite particles are of core-shell structure with spherical shape and the shell thickness is about 10 nm. X-ray powder diffraction results indicate that the interlayer spacing of IF-WS{sub 2} shell decreases and approaches that of 2H-WS{sub 2} with increasing annealing temperatures, representing an expansion of 3.3-1.6%. Amore » mechanism of IF-WS{sub 2} formation via sulfur diffusion into fullerene nanoparticles is discussed. Thermal analysis shows that the nanoparticles obtained at different temperatures exhibit similar thermal stability and the onset temperature of oxidization is about 410 deg. C. Encapsulating hard tungsten core into IF-WS{sub 2} and the spherical shape of the core-shell structures may enhance their performance in tribological applications.« less
Baziulyte-Paulaviciene, Dovile; Karabanovas, Vitalijus; Stasys, Marius; Jarockyte, Greta; Poderys, Vilius; Sakirzanovas, Simas; Rotomskis, Ricardas
2017-01-01
Upconverting nanoparticles (UCNPs) are promising, new imaging probes capable of serving as multimodal contrast agents. In this study, monodisperse and ultrasmall core and core-shell UCNPs were synthesized via a thermal decomposition method. Furthermore, it was shown that the epitaxial growth of a NaGdF 4 optical inert layer covering the NaGdF 4 :Yb,Er core effectively minimizes surface quenching due to the spatial isolation of the core from the surroundings. The mean diameter of the synthesized core and core-shell nanoparticles was ≈8 and ≈16 nm, respectively. Hydrophobic UCNPs were converted into hydrophilic ones using a nonionic surfactant Tween 80. The successful coating of the UCNPs by Tween 80 has been confirmed by Fourier transform infrared (FTIR) spectroscopy. Scanning electron microscopy (SEM), powder X-ray diffraction (XRD), photoluminescence (PL) spectra and magnetic resonance (MR) T1 relaxation measurements were used to characterize the size, crystal structure, optical and magnetic properties of the core and core-shell nanoparticles. Moreover, Tween 80-coated core-shell nanoparticles presented enhanced optical and MR signal intensity, good colloidal stability, low cytotoxicity and nonspecific internalization into two different breast cancer cell lines, which indicates that these nanoparticles could be applied as an efficient, dual-modal contrast probe for in vivo bioimaging.
Zhang, Lu; Sun, Jiashu; Wang, Yilian; Wang, Jiancheng; Shi, Xinghua; Hu, Guoqing
2016-07-19
We report a nonspecific organelle-targeting strategy through one-step microfluidic fabrication and screening of a library of surface charge- and lipid components/ratios-varied lipid shell-polymer core nanoparticles. Different from the common strategy relying on the use of organelle-targeted moieties conjugated onto the surface of nanoparticles, here, we program the distribution of hybrid nanoparticles in lysosomes or mitochondria by tuning the lipid components/ratios in shell. Hybrid nanoparticles with 60% 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) and 20% 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine (DOPE) can intracellularly target mitochondria in both in vitro and in vivo models. While replacing DOPE with the same amount of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC), the nanoparticles do not show mitochondrial targeting, indicating an incremental effect of cationic and fusogenic lipids on lysosomal escape which is further studied by molecular dynamics simulations. This work unveils the lipid-regulated subcellular distribution of hybrid nanoparticles in which target moieties and complex synthetic steps are avoided.
Synthesis of bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles
Li, Xue-Mei; Liu, Hong-Ling; Liu, Xiao; Fang, Ning; Wang, Xian-Hong; Wu, Jun-Hua
2015-01-01
Bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles were synthesized by a modified nanoemulsion process using poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO) as the surfactant. The morphology and crystal structure of the nanoparticles were studied by TEM/HRTEM and XRD. The nanoparticles manifest soft ferromagnetic and/or near superparamagnetic behavior with a small coercivity of ~19 Oe at room temperature. The corresponding magnetic hysteresis curves were elucidated by the modified Langevin equation. The FTIR study confirms the PEO-PPO-PEO molecules on the surface of the nanoparticles. The UV-vis and PL results reveal the well-behaved absorption bands including surface plasmon resonance and multiple visible fingerprint photoluminescent emissions of the nanoparticles dispersed in both hydrophilic and hydrophobic solvents. Moreover, the processes of solvent dispersion-collection of the nanoparticles were demonstrated for application readiness of such core-shell nanostructures. PMID:26548369
Synthesis of bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles
NASA Astrophysics Data System (ADS)
Li, Xue-Mei; Liu, Hong-Ling; Liu, Xiao; Fang, Ning; Wang, Xian-Hong; Wu, Jun-Hua
2015-11-01
Bi-phase dispersible core-shell FeAu@ZnO magneto-opto-fluorescent nanoparticles were synthesized by a modified nanoemulsion process using poly(ethylene glycol)-block-poly(propylene glycol)-block-poly(ethylene glycol) (PEO-PPO-PEO) as the surfactant. The morphology and crystal structure of the nanoparticles were studied by TEM/HRTEM and XRD. The nanoparticles manifest soft ferromagnetic and/or near superparamagnetic behavior with a small coercivity of ~19 Oe at room temperature. The corresponding magnetic hysteresis curves were elucidated by the modified Langevin equation. The FTIR study confirms the PEO-PPO-PEO molecules on the surface of the nanoparticles. The UV-vis and PL results reveal the well-behaved absorption bands including surface plasmon resonance and multiple visible fingerprint photoluminescent emissions of the nanoparticles dispersed in both hydrophilic and hydrophobic solvents. Moreover, the processes of solvent dispersion-collection of the nanoparticles were demonstrated for application readiness of such core-shell nanostructures.
NASA Astrophysics Data System (ADS)
Belousov, A. V.; Morozov, V. N.; Krusanov, G. A.; Kolyvanova, M. A.; Chernyaev, A. P.; Shtil, A. A.
2018-03-01
The Monte Carlo method (computer simulation) is used to construct a physical model of secondary particles emission induced by the simulated irradiation of a gold nanoparticle with 60Co. It is demonstrated that the modification of the nanoparticle surface with polyethylene glycol affects the spectrum of secondary electrons produced in a nanoparticle and leaving it and its shell. The model takes into account the size and the chemical composition of the shell and provides an opportunity to design antitumor radiosensitizers based on gold nanoparticles.
Core-Shell Photonic Nanoparticles for Enhanced Solar-to-Fuel Photocatalytic Conversion
2017-10-11
photocatalytic activity of semiconducting materials. They synthesized and functionalized titanium dioxide nanoparticles with a partial shell of gold...Their research also characterized the photocatalytic activity . The second area was the tuning the dielectric environment of the nanoparticles with think...successful investigation of bimetallic nanoshells that enhance the photocatalytic activity of semiconducting materials. Our earlier work focused on the
Gründer, Y; Ramasse, Q M; Dryfe, R A W
2015-02-28
Copper on gold forms a monolayer deposit via underpotential deposition. For gold particles adsorbed at a liquid-liquid interface this results in a uniform one monolayer thick shell. This approach offers a new route for the uniform functionalisation of nanoparticles and presents a way to probe fundamental processes that underlie nanoparticle synthesis.
Park, Minsung; Seo, Sungmin; Lee, Soo Jin; Jung, Jong Hwa
2010-11-01
Fluorogenic based nitrobenzofuran-functionalized Ni@SiO(2) core/shell magnetic nanoparticles have been prepared by sol-gel grafting reaction. Their ability to detect and remove metal ions was evaluated by fluorophotometry. The nanoparticles exhibited a high affinity and selectivity for Cu(2+) over competing metal ions. Furthermore, the nanoparticles efficiently removed Cu(2+) in drinking water and human blood.
Supercritical fluid technology of nanoparticle coating for new ceramic materials.
Aymonier, Cyril; Elissalde, Catherine; Reveron, Helen; Weill, François; Maglione, Mario; Cansell, François
2005-06-01
This work highlights, for the first time, the coating of ferroelectric nanoparticles with a chemical fluid deposition process in supercritical fluids. BaTiO3 nanoparticles of about 50 nm are coated with a shell of a few nanometers of amorphous alumina and can be recovered as a dry powder for processing. The sintering of these core-shell nanoparticles gives access to a ceramic material with very interesting ferroelectric properties, in particular, dielectric losses below 1%.
Sustained release of methotrexate through liquid-crystalline folate nanoparticles.
Misra, Rahul; Mohanty, Sanat
2014-09-01
To make chemotherapy more effective, sustained release of the drug is desirable. By controlling the release rates, constant therapeutic levels can be achieved which can avoid re-administration of drug. This helps to combat tumors more effectively with minimal side effects. The present study reports the control release of methotrexate through liquid-crystalline folate nanoparticles. These nanoparticles are composed of highly ordered folate self-assembly which encapsulate methotrexate molecules. These drug molecules can be released in a controlled manner by disrupting this assembly in the environment of monovalent cations. The ordered structure of folate nanoparticles offers low drug losses of about 4-5%, which is significant in itself. This study reports the size-control method of forming methotrexate encapsulated folate nanoparticles as well as the release of methotrexate through these nanoparticles. It has been demonstrated that methotrexate release rates can be controlled by controlling the size of the nanoparticles, cross-linking cation and cross-linking concentration. The effect of different factors like drug loading, release medium, and pH of the medium on methotrexate release rates was also studied.
NASA Astrophysics Data System (ADS)
Prow, Tarl W.; Yamada, Miko; Dang, Nhung; Evans, Conor L.
2017-02-01
The purpose of this research was to develop advanced imaging approaches to characterise the combination of elongated silica microparticles (EMP) and nanoparticles to control topical delivery of drugs and peptides. The microparticles penetrate through the epidermis and stop at the dermal-epidermal junction (DEJ). In this study we incorporated a fluorescent lipophilic dye, DiI, as a hydrophobic drug surrogate into the nanoparticle for visualization with microscopy. In another nanoparticle-based approach we utilized a chemically functionalized melanin nanoparticle for peptide delivery. These nanoparticles were imaged by coherent anti-Stoke Raman scattering (CARS) microscopy to characterize the delivery of these nanoparticles into freshly excised human skin. We compared four different coating approaches to combine EMP and nanoparticles. These data showed that a freeze-dried formulation with cross-linked alginate resulted in 100% of the detectable nanoparticle retained on the EMP. When this dry form of EMP-nanoparticle was applied to excised, living human abdominal skin, the EMP penetrated to the DEJ followed by controlled release of the nanoparticles. This formulation resulted in a sustained release profile, whereas a freeze-dried formulation without crosslinking showed an immediate burst-type release profile. These data show that advanced imaging techniques can give unique, label free data that shows promise for clinical investigations.
NASA Astrophysics Data System (ADS)
Santagata, A.; Guarnaccio, A.; Pietrangeli, D.; Szegedi, Á.; Valyon, J.; De Stefanis, A.; De Bonis, A.; Teghil, R.; Sansone, M.; Mollica, D.; Parisi, G. P.
2015-05-01
Ultra-short pulsed laser ablation of materials in liquid has been demonstrated to be a versatile technique for nanoparticles production. In a previous paper, it has been described, for the first time, how by laser ablation in a liquid system, silver nanoparticles can be loaded onto SBA-15 and MCM-41 supports which show promising catalytic properties for the oxidation of Volatile Organic Compounds (VOCs). The aim of the present research is to demonstrate the formation of stable silver-silica core-shell nanoparticles by direct laser ablation (Ti:Sa; 800 nm pulse duration: 120 fs repetition rate: 1 kHz, pulse energy: 3.6 mJ, fluence: 9 J cm - 2) of a Ag target submerged in a static colloidal solution of MCM-41 or SBA-15 silica nanoporous materials. In previous studies, it was discovered that a side and negligible product of the laser ablation process of silver performed in water-silica systems, could be related to the formation of silver-silica core-shell nanoparticles. In order to emphasize this side process some modifications to the laser ablation experimental set-up were performed. Among these, the most important one, in order to favor the production of the core-shell systems, was to keep the liquid silica suspension firm. The laser generated nanomaterials were then analyzed using TEM morphologic characterization. By UV-vis absorption spectra the observed features have been related to components of the colloidal solution as well as to the number of the incident laser pulses. In this manner characterizations on both the process and the resulting suspension have been performed. Significant amount of small sized silver-silica core-shell nanoparticles have been detected in the studied systems. The size distribution, polydispersivity, UV-vis plasmonic bands and stability of the produced silver-silica core-shell nanocomposites have been related to the extent of damage induced in the nanoporous silica structure during the ablation procedure adopted here. In presence of SBA-15 the silver-silica core-shell nanoparticles observed by TEM are smaller and more homogeneously dispersed if compared with the core-shell system obtained when the MCM-41 mesoporous silica was used. The outcomes show that the choice of the mesoporous silica material can affect the silica shell thickness in addition to the Ag NPs size distribution. With this regard, TEM images evidence that in MCM-41 the silver-silica core-shell nanostructures display a silica layer thickness between 1-10 nm conversely, for SBA-15, the silver-silica core-shell nanoparticles are finely dispersed and the silica shell shows, when present, an average thickness of about 5 nm.
Memory effect versus exchange bias for maghemite nanoparticles
NASA Astrophysics Data System (ADS)
Nadeem, K.; Krenn, H.; Szabó, D. V.
2015-11-01
We studied the temperature dependence of memory and exchange bias effects and their dependence on each other in maghemite (γ-Fe2O3) nanoparticles by using magnetization studies. Memory effect in zero field cooled process in nanoparticles is a fingerprint of spin-glass behavior which can be due to i) surface disordered spins (surface spin-glass) and/or ii) randomly frozen and interacting nanoparticles core spins (super spin-glass). Temperature region (25-70 K) for measurements has been chosen just below the average blocking temperature (TB=75 K) of the nanoparticles. Memory effect (ME) shows a non-monotonous behavior with temperature. It shows a decreasing trend with decreasing temperature and nearly vanishes below 30 K. However it also decreased again near the blocking temperature of the nanoparticles e.g., 70 K. Exchange bias (EB) in these nanoparticles arises due to core/shell interface interactions. The EB increases sharply below 30 K due to increase in core/shell interactions, while ME starts vanishing below 30 K. We conclude that the core/shell interface interactions or EB have not enhanced the ME but may reduce it in these nanoparticles.
Dreyer, Axel; Feld, Artur; Kornowski, Andreas; Yilmaz, Ezgi D; Noei, Heshmat; Meyer, Andreas; Krekeler, Tobias; Jiao, Chengge; Stierle, Andreas; Abetz, Volker; Weller, Horst; Schneider, Gerold A
2016-05-01
It is commonly accepted that the combination of the anisotropic shape and nanoscale dimensions of the mineral constituents of natural biological composites underlies their superior mechanical properties when compared to those of their rather weak mineral and organic constituents. Here, we show that the self-assembly of nearly spherical iron oxide nanoparticles in supercrystals linked together by a thermally induced crosslinking reaction of oleic acid molecules leads to a nanocomposite with exceptional bending modulus of 114 GPa, hardness of up to 4 GPa and strength of up to 630 MPa. By using a nanomechanical model, we determined that these exceptional mechanical properties are dominated by the covalent backbone of the linked organic molecules. Because oleic acid has been broadly used as nanoparticle ligand, our crosslinking approach should be applicable to a large variety of nanoparticle systems.
Thermal annealing dynamics of carbon-coated LiFePO4 nanoparticles studied by in-situ analysis
NASA Astrophysics Data System (ADS)
Krumeich, Frank; Waser, Oliver; Pratsinis, Sotiris E.
2016-10-01
The thermal behavior of core-shell carbon-coated lithium iron phosphate (LiFePO4-C) nanoparticles made by flame spray pyrolysis (FSP) during annealing was investigated by in-situ transmission electron microscopy (TEM), in-situ X-ray powder diffraction (XRD) as well as ex-situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS). Crystallization of the initially glassy LiFePO4-C nanoparticles starts at quite low temperatures (T=400 °C), forming single crystals inside the confinement of the carbon shell. Upon increasing the temperature to T≥700 °C, LiFePO4 starts to diffuse through the carbon shell resulting in cavities inside the mostly intact carbon shell. By increasing the temperature further to T≥800 °C, the initial core-shell morphology converts into open carbon shells (flakes and cenospheres) and bulky LiFePO4 particles (diameter in the range 300-400 nm), in agreement with ex-situ experiments.
Liao, Xue; Chen, Yanhua; Qin, Meihong; Chen, Yang; Yang, Lei; Zhang, Hanqi; Tian, Yuan
2013-12-15
In this paper, Au-Ag-Au double shell nanoparticles were prepared based on the reduction of the metal salts HAuCl4 and AgNO3 at the surface of seed particles. Due to the synergistic effect between Au and Ag, the hybrid nanoparticles are particularly stable and show excellent performances on the detection of 2-mercapto-1-methylimidazole (methimazole). The binding of target molecule at the surface of Au-Ag-Au double shell nanoparticles was demonstrated based on both localized surface plasmon resonance (LSPR) and surface-enhanced Raman scattering (SERS) spectra. The LSPR intensity is directly proportional to the methimazole concentration in the range of 0.10-3.00×10(-7) mol L(-1). The SERS spectrum can be applied in identification of methimazole molecule. The LSPR coupled with SERS based on the Au-Ag-Au double shell nanoparticles would be very attractive for the quantitative determination and qualitative analysis of the analytes in medicines. © 2013 Elsevier B.V. All rights reserved.
Kim, Hyung Joon; Lee, Sun-Mi; Park, Kyu-Hyung; Mun, Chin Hee; Park, Yong-Beom; Yoo, Kyung-Hwa
2015-08-01
We have developed methotrexate (MTX)-loaded poly(lactic-co-glycolic acid, PLGA) gold (Au)/iron (Fe)/gold (Au) half-shell nanoparticles conjugated with arginine-glycine-aspartic acid (RGD), which can be applied for magnetic targeted chemo-photothermal treatment, and in vivo multimodal imaging of rheumatoid arthritis (RA). Upon near-infrared (NIR) irradiation, local heat is generated at the inflammation region due to the NIR resonance of Au half-shells and MTX release from PLGA nanoparticles is accelerated. The Fe half-shell layer embedded between the Au half-shell layers enables in vivo T2-magnetic resonance (MR) imaging in addition to NIR absorbance imaging. Furthermore, the delivery of the nanoparticles to the inflammation region in collagen-induced arthritic (CIA) mice, and their retention can be enhanced under external magnetic field. When combined with consecutive NIR irradiation and external magnetic field application, these nanoparticles provide enhanced therapeutic effects with an MTX dosages of only 0.05% dosage compared to free MTX therapy for the treatment of RA. Copyright © 2015 Elsevier Ltd. All rights reserved.
Shao, Wei; Chen, Guanying; Damasco, Jossana; Wang, Xianliang; Kachynski, Aliaksandr; Ohulchanskyy, Tymish Y; Yang, Chunhui; Ågren, Hans; Prasad, Paras N
2014-03-15
In this work, we report on efficient visible and near-IR upconversion emissions in colloidal hexagonal-phase core/shell NaYF4:Er(3+)/NaYF4 nanoparticles (∼38 nm) under IR laser excitation at 1523 nm. Varying amounts of Er(3+) dopants were introduced into the core NaYF4:Er(3+) nanoparticles, revealing an optimized Er(3+) concentration of 10% for the highest luminescent efficiency. An inert epitaxial shell layer of NaYF4 grown onto the core of the NaYF4:Er(3+) 10% nanoparticle increased its upconversion emission intensity fivefold due to suppression of surface-related quenching mechanisms, yielding the absolute upconversion efficiency to be as high as ∼3.9±0.3% under an excitation density of 18 W/cm(2). The dependence of the intensity of upconversion emission peaks on laser excitation density in the core/shell nanoparticle displayed "saturation effects" at low excitation density in the range of 1.5-18 W/cm(2), which again demonstrates high upconversion efficiency.
Core–shell nanoparticles: synthesis and applications in catalysis and electrocatalysis
Core–shell nanoparticles (CSNs) are a class of nanostructured materials that have recently received increased attention owing to their interesting properties and broad range of applications in catalysis, biology, materials chemistry and sensors. By rationally tuning the cores as ...
Hollow nanoparticle cathode materials for sodium electrochemical cells and batteries
Shevchenko, Elena; Rajh, Tijana; Johnson, Christopher S.; Koo, Bonil
2016-07-12
A cathode comprises, in its discharged state, a layer of hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles disposed between two layers of carbon nanotubes, and preferably including a metallic current collector in contact with one of the layers of carbon nanotubes. Individual particles of the hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles comprise a crystalline shell of .gamma.-Fe.sub.2O.sub.3 including cation vacancies within the crystal structure of the shell (i.e., iron vacancies of anywhere between 3% to 90%, and preferably 44 to 77% of available octahedral iron sites). Sodium ions are intercalated within at least some of the cation vacancies within the crystalline shell of the hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles.
Surface and exchange-bias effects in compacted CaMnO3-δ nanoparticles
NASA Astrophysics Data System (ADS)
Markovich, V.; Fita, I.; Wisniewski, A.; Puzniak, R.; Mogilyansky, D.; Titelman, L.; Vradman, L.; Herskowitz, M.; Gorodetsky, G.
2008-02-01
Magnetic properties of compacted 50nm CaMnO3-δ (CMO) nanoparticles have been investigated. Measurements of ac-susceptibility exhibit upon cooling two magnetic transitions at Ttilde 270K accompanied by a small spontaneous magnetic moment and a para-antiferromagnetic (AFM) transition at TN˜120K , observed previously in bulk CMO. Asymmetric magnetization hysteresis loops observed in applied magnetic fields H≤90kOe are attributed to an exchange coupling between the antiferromagnetic core and the ferromagnetic (FM) shell of the CMO nanoparticles. This work provides the observation of exchange bias effect in manganite nanoparticles with inverted AFM-core-FM-shell structure, as compared to the typical FM-core-AFM-shell. Effects of surface and exchange anisotropy are also discussed.
NASA Astrophysics Data System (ADS)
Crisan, A. D.; Angelakeris, M.; Simeonidis, K.; Tsiaoussis, I.; Crisan, O.
2010-11-01
In core-shell systems with non-magnetic core and magnetic shell, the electron transport and magnetic properties are expected to show enhanced behavior due to the particular morpho-structural features of the conductive and magnetic regions. This may lead to novel advanced GMR materials and spin valves. This is the case of core-shell Ag-Co colloidal nanoscale particles that organize into regular arrays. An insight on the structure and morphology of the newly synthesized Ag-Co nanoparticles deposited on different substrates will be presented. The influence of the substrate on different morphologies and organization dynamics is discussed. It is shown that the magnetic behavior of the Ag-Co nanoparticles is highly influenced by the corona-like morphology of Co shell, chemical environment of the magnetic atoms and by the fact that they exhibit strongly reduced coordination due to the surface states.
Ratanajanchai, Montri; Soodvilai, Sunhapas; Pimpha, Nuttaporn; Sunintaboon, Panya
2014-01-01
Herein, we prepared PEI-immobilized core-shell particles possessing various types of polymer cores via a visible light-induced surfactant-free emulsion polymerization (SFEP) of three vinyl monomers: styrene (St), methyl methacrylate (MMA), and 2-hydroxyethyl methacrylate (HEMA). An effect of monomers on the polymerization and characteristics of resulting products was investigated. Monomers with high polarity can provide high monomer conversion, high percentage of grafted PEI, stable particles with uniform size distribution but less amino groups per particles. All prepared nanoparticles exhibited a core-shell nanostructure, containing PEI on the shell with hydrodynamic size around 140-230nm. For in-vitro study in Caco-2 cells, we found that the incorporation of PEI into these core-shell nanoparticles can significantly reduce its cytotoxic effect and also be able to internalized within the cells. Accordingly, these biocompatible particles would be useful for various biomedical applications, including gene transfection and intracellular drug delivery. © 2013.
El-Naggar, Mehrez E; Shaheen, Tharwat I; Fouda, Moustafa M G; Hebeish, Ali A
2016-01-20
Herein, we present a new approach for the synthesis of gold nanoparticles (AuNPs) individually and as bimetallic core-shell nanoparticles (AgNPs-AuNPs). The novelty of the approach is further maximized by using curdlan (CRD) biopolymer to perform the dual role of reducing and capping agents and microwave-aided technology for affecting the said nanoparticles with varying concentrations in addition to those affected by precursor concentrations. Thus, for preparation of AuNPs, curdlan was solubilized in alkali solution followed by an addition of tetrachloroauric acid (HAuCl4). The curdlan solution containing HAuCl4 was then subjected to microwave radiation for up to 10 min. The optimum conditions obtained with the synthesis of AuNPs were employed for preparation of core-shell silver-gold nanoparticles by replacing definite portion of HAuCl4 with an equivalent portion of silver nitrate (AgNO3). The portion of AgNO3 was added initially and allowed to be reduced by virtue of the dual role of curdlan under microwave radiation. The corresponding portion of HAuCl4 was then added and allowed to complete the reaction. Characterization of AuNPs and AgNPs-AuNPs core-shell were made using UV-vis spectra, TEM, FTIR, XRD, zeta potential, and AFM analysis. Accordingly, strong peaks of the colloidal particles show surface plasmon resonance (SPR) at maximum wavelength of 540 nm, proving the formation of well-stabilized gold nanoparticles. TEM investigations reveal that the major size of AuNPs formed at different Au(+3)concentration lie below 20 nm with narrow size distribution. Whilst, the SPR bands of AgNPs-AuNPs core-shell differ than those obtained from original AgNPs (420 nm) and AuNPs (540 nm). Such shifting due to SPR of Au nanoshell deposited onto AgNPs core was significantly affected by the variation of bimetallic ratios applied. TEM micrographs show variation in contrast between dark silver core and the lighter gold shell. Increasing the ratio of silver ions leads to significant decrease in zeta potential of the formed bimetallic core-shell. FT-IR discloses the interaction between CRD and metal nanoparticles, which could be the question of reducing and stabilizing metal and bimetallic nanoparticles. XRD patterns assume insufficient difference for the AuNPs and AgNPs-AuNPs core-shell samples due to close lattice constants of Ag and Au. Based on AFM, AuNPs and AgNPs-AuNPs core-shell exhibited good monodispersity with spherical particles possessing different sizes in the studied samples. The average sizes of both metal and bimetallic core-shell were found to be 52 and 45 nm, respectively. Copyright © 2015 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Zou, Haixia; Jin, Fengmin; Song, Xiaoyan; Xing, Jinfeng
2017-04-01
The introduction of a thick shell structure has been widely used to enhance the emission intensity of upconversion nanoparticles (UCNPs). However, a thick shell could increase the distance between UCNPs and photosensitizers, which is not favourable to the generation of singlet oxygen (1O2) in photodynamic therapy (PDT) due to the low fluorescence resonance energy transfer (FRET) efficiency. In this study, we used a facile method to prepare UCNPs that the emission intensity could increase with the shell thickness decreasing, which facilitated the efficient FRET between UCNPs and photosensitizers. In detail, the Nd3+-doped UCNPs with different dopant concentration of Yb3+ were prepared and characterized firstly. The Ir/g (intensity of red luminescence to green luminescence) was tuned to increase largely by precisely controlling Yb3+ concentration in core-shell, which could make UCNPs effectively activate methylene blue (MB). Then, a unique procedure was used to prepare NaYF4:Yb/Er/Nd@NaYF4:Nd (Yb3+:30%) core-shell nanoparticles with different shell thickness by tuning the amount of the core. The upconversion luminescence (UCL) intensity of those UCNPs enhanced dramatically with the shell thickness decreasing. Furthermore, UCNPs and MB were encapsulated into SiO2 nanoparticles. FRET efficiency between UCNPs and MB largely increased with the shell thickness of UCNPs decreasing. Correspondingly, the efficiency of 1O2 generation obviously increased. We provided a new method to optimize the UCL intensity and FRET efficiency at the same time to produce 1O2 efficiently.
NASA Astrophysics Data System (ADS)
Carrião, Marcus S.; Bakuzis, Andris F.
2016-04-01
The phenomenon of heat dissipation by magnetic materials interacting with an alternating magnetic field, known as magnetic hyperthermia, is an emergent and promising therapy for many diseases, mainly cancer. Here, a magnetic hyperthermia model for core-shell nanoparticles is developed. The theoretical calculation, different from previous models, highlights the importance of heterogeneity by identifying the role of surface and core spins on nanoparticle heat generation. We found that the most efficient nanoparticles should be obtained by selecting materials to reduce the surface to core damping factor ratio, increasing the interface exchange parameter and tuning the surface to core anisotropy ratio for each material combination. From our results we propose a novel heat-based hyperthermia strategy with the focus on improving the heating efficiency of small sized nanoparticles instead of larger ones. This approach might have important implications for cancer treatment and could help improving clinical efficacy.The phenomenon of heat dissipation by magnetic materials interacting with an alternating magnetic field, known as magnetic hyperthermia, is an emergent and promising therapy for many diseases, mainly cancer. Here, a magnetic hyperthermia model for core-shell nanoparticles is developed. The theoretical calculation, different from previous models, highlights the importance of heterogeneity by identifying the role of surface and core spins on nanoparticle heat generation. We found that the most efficient nanoparticles should be obtained by selecting materials to reduce the surface to core damping factor ratio, increasing the interface exchange parameter and tuning the surface to core anisotropy ratio for each material combination. From our results we propose a novel heat-based hyperthermia strategy with the focus on improving the heating efficiency of small sized nanoparticles instead of larger ones. This approach might have important implications for cancer treatment and could help improving clinical efficacy. Electronic supplementary information (ESI) available: Unit cells per region calculation; core-shell Hamiltonian; magnetisation description functions; energy argument of Brillouin function; polydisperse models; details of experimental procedure; LRT versus core-shell model; model calculation software; and shell thickness study. See DOI: 10.1039/C5NR09093H
Singh, Nimisha; Patel, Khushbu; Sahoo, Suban K; Kumar, Rajender
2018-03-01
Nitric oxide releasing superparamagnetic (Fe 3 O 4 -Au@NTHP) nanoparticles were synthesized by conjugation of human biomarker of nitric oxide, N-nitrosothioproline with iron oxide-gold (Fe 3 O 4 -Au) core shell nanoparticles. The structure and morphology of the prepared nanoparticles were confirmed by ATR-FTIR, HR-TEM, EDAX, XPS, DLS and VSM measurements. N-nitrosothioproline is a natural molecule and nontoxic to humans. Thus, the core shell nanoparticles prepared were highly biocompatible. The prepared Fe 3 O 4 -Au@NTHP nanoparticles also provided an excellent release of nitric oxide in dark and upon light irradiation for cancer treatment. The amount of NO release was controllable with the wavelength of light and time of irradiation. The developed nanoparticles provided efficient cellular uptake and good cytotoxicity in picomolar range when tested on HeLa cancerous cells. These nanoparticles on account of their controllable NO release can also be used to release small amount of NO for killing cancerous cells without any toxic effect. Furthermore, the magnetic and photochemical properties of these nanoparticles provides dual platform for magneto therapy and phototherapy for cancer treatment. Copyright © 2017 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Wei, Chao; Xu, Min-Min; Fang, Cong-Wei; Jin, Qi; Yuan, Ya-Xian; Yao, Jian-Lin
2017-03-01
Traditional "sandwich" structure immunoassay is mainly based on the self-assembly of "antibody on solid substrate-antigen-antibody with nanotags" architectures, and the sensitivity of this strategy is critically depended on the surface enhanced Raman scattering (SERS) activities and stability of nanotags. Therefore, the rational design and fabrication on the SERS nanotags attracts the common interests to the bio-related detecting and imaging. Herein, silica encapsulated Au with mercaptobenzoic acid (MBA) core-shell nanoparticles (Au-MBA@SiO2) are fabricated instead of the traditional naked Au or Ag nanoparticles for the SERS-based immunoassay on human and mouse IgG antigens. The MBA molecules facilitate the formation of continuous pinhole-free silica shell and are also used as SERS labels. The silica shell is employed to protect MBA labels and to isolate Au core from the ambient solution for blocking the aggregation. This shell also played the similar role to BSA in inhibiting the nonspecific bindings, which allowed the procedures for constructing "sandwich" structures to be simplified. All of these merits of the Au-MBA@SiO2 brought the high performance in the related immunoassay. Benefiting from the introduction of silica shell to encapsulate MBA labels, the detection sensitivity was improved by about 1- 2 orders of magnitude by comparing with the traditional approach based on naked Au-MBA nanoparticles. This kind of label-embedded core-shell nanoparticles could be developed as the versatile nanotags for the bioanalysis and bioimaging.
He, Zelai; Huang, Jingwen; Xu, Yuanyuan; Zhang, Xiangyu; Teng, Yanwei; Huang, Can; Wu, Yufeng; Zhang, Xi; Zhang, Huijun; Sun, Wenjie
2015-12-08
An amphiphilic copolymer, folic acid (FA) modified poly(ethylene glycol)-poly(lactic-co-glycolic acid) (FA-PEG-PLGA) was prepared and explored as a nanometer carrier for the co-delivery of cisplatin (cis-diaminodichloroplatinum, CDDP) and paclitaxel (PTX). CDDP and PTX were encapsulated inside the hydrophobic inner core and chelated to the middle shell, respectively. PEG provided the outer corona for prolonged circulation. An in vitro release profile of the CDDP + PTX-encapsulated nanoparticles revealed that the PTX chelation cross-link prevented an initial burst release of CDDP. After an incubation period of 24 hours, the CDDP+PTX-encapsulated nanoparticles exhibited a highly synergistic effect for the inhibition of A549 (FA receptor negative) and M109 (FA receptor positive) lung cancer cell line proliferation. Pharmacokinetic experiment and distribution research shows that nanoparticles have longer circulation time in the blood and can prolong the treatment times of chemotherapeutic drugs. For the in vivo treatment of A549 cells xeno-graft lung tumor, the CDDP+PTX-encapsulated nanoparticles displayed an obvious tumor inhibiting effect with an 89.96% tumor suppression rate (TSR). This TSR was significantly higher than that of free chemotherapy drug combination or nanoparticles with a single drug. For M109 cells xeno-graft tumor, the TSR was 95.03%. In vitro and in vivo experiments have all shown that the CDDP+PTX-encapsulated nanoparticles have better targeting and antitumor effects in M109 cells than CDDP+PTX-loaded PEG-PLGA nanoparticles (p < 0.05). In addition, more importantly, the enhanced anti-tumor efficacy of the CDDP+PTX-encapsulated nanoparticles came with reduced side-effects. No obvious body weight loss or functional changes occurred within blood components, liver, or kidneys during the treatment of A549 and M109 tumor-bearing mice with the CDDP+PTX-encapsulated nanoparticles. Thus, the FA modified amphiphilic copolymer-based combination of CDDP and PTX may provide useful guidance for effective and safe cancer chemotherapy, especially in tumors with high FA receptor expression.
2014-08-19
Box 12211 Research Triangle Park, NC 27709-2211 Core-shell nanoparticles, frrite, ferroelectric , magnetoelectric REPORT DOCUMENTATION PAGE 11...of ferrite- ferroelectric core-shell nanofibers and studies on magneto- electric interactions Appl. Phys. Lett. 104, 052910 (2014); 10.1063/1.4864113...1.4893699] A ferromagnetic- ferroelectric composite is a multiferroic in which the magneto-electric (ME) interaction is facilitated by mechanical forces.1–6
Tian, Xinlong; Tang, Haibo; Luo, Junming; ...
2017-04-25
A class of core–shell structured low-platinum catalysts with well-dispersed inexpensive titanium copper nitride nanoparticles as cores and atomic platinum layers as shells exhibiting high activity and stability for the oxygen reduction reaction is successfully developed. In using nitrided carbon nanotubes (NCNTs) as the support greatly improved the morphology and dispersion of the nitride nanoparticles, resulting in significant enhancement of the performance of the catalyst. The optimized catalyst, Ti 0.9Cu 0.1N@Pt/NCNTs, has a Pt mass activity 5 times higher than that of commercial Pt/C, comparable to that of core–shell catalysts with precious metal nanoparticles as the core, and much higher thanmore » that the latter if we take into account the mass activity of all platinum group metals. Furthermore, only a minimal loss of activity can be observed after 10000 potential cycles, demonstrating the catalyst’s high stability. After durability testing, atomic-scale elemental mapping confirmed that the core–shell structure of the catalyst remained intact. This approach may open a pathway for the design and preparation of high-performance inexpensive core–shell catalysts for a wide range of applications in energy conversion processes.« less
NASA Astrophysics Data System (ADS)
Fang, Jiasheng; Zhang, Yiwei; Zhou, Yuming; Zhao, Shuo; Zhang, Chao; Huang, Mengqiu; Gao, Yan
2017-08-01
Novel NiO-TiO2 hybrids/mSiO2 yolk-shell architectures loaded with ultrasmall Au nanoparticles (STNVS-Au) were developed via the rational synthetic strategy. The hierarchical yolk-shell nanostructures (STNVS) with high surface areas were constructed by a facile "bottom-up" assembly process using SiO2 materials and polymer resins as cores/shells and sacrificial templates, accompanied by a simple hydrothermal incorporation of NiO into uniform amorphous TiO2 layers that were converted to NiO-anatase TiO2 p-n heterojunction hybrids. Then, numerous sub-3 nm Au nanoparticles were post encapsulated within STNVS nanostructures through the low-temperature hydrogen reduction based on the unique deposition-precipitation method with Au(en)2Cl3 compounds as gold precursors. The NiO-TiO2 hybrids alloying with Au nanoparticles were effectively protected and entrapped within STNVS architectures, and interacted with outer mSiO2-Au shells, which comprised the powerful STNVS-Au yolk-shell nanoreactors and produced stronger configural synergies in enhancing the heterogeneous catalysis. Into catalyzing the reduction of 4-nitrophenol to 4-aminophenol, the STNVS-Au was shown with outstanding activity and reusability, and its pristine morphology was well retained during the recycling process.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Tian, Xinlong; Tang, Haibo; Luo, Junming
A class of core–shell structured low-platinum catalysts with well-dispersed inexpensive titanium copper nitride nanoparticles as cores and atomic platinum layers as shells exhibiting high activity and stability for the oxygen reduction reaction is successfully developed. In using nitrided carbon nanotubes (NCNTs) as the support greatly improved the morphology and dispersion of the nitride nanoparticles, resulting in significant enhancement of the performance of the catalyst. The optimized catalyst, Ti 0.9Cu 0.1N@Pt/NCNTs, has a Pt mass activity 5 times higher than that of commercial Pt/C, comparable to that of core–shell catalysts with precious metal nanoparticles as the core, and much higher thanmore » that the latter if we take into account the mass activity of all platinum group metals. Furthermore, only a minimal loss of activity can be observed after 10000 potential cycles, demonstrating the catalyst’s high stability. After durability testing, atomic-scale elemental mapping confirmed that the core–shell structure of the catalyst remained intact. This approach may open a pathway for the design and preparation of high-performance inexpensive core–shell catalysts for a wide range of applications in energy conversion processes.« less
Das, Sourav; Ranjana, Neha; Misra, Ananyo Jyoti; Suar, Mrutyunjay; Mishra, Amrita; Tamhankar, Ashok J; Lundborg, Cecilia Stålsby; Tripathy, Suraj K
2017-07-10
Water borne pathogens present a threat to human health and their disinfection from water poses a challenge, prompting the search for newer methods and newer materials. Disinfection of the Gram-negative bacterium Escherichia coli and the Gram-positive coccal bacterium Staphylococcus aureus in an aqueous matrix was achieved within 60 and 90 min, respectively, at 35 °C using solar-photocatalysis mediated by sonochemically synthesized Ag@ZnO core-shell nanoparticles. The efficiency of the process increased with the increase in temperature and at 55 °C the disinfection for the two bacteria could be achieved in 45 and 60 min, respectively. A new ultrasound-assisted chemical precipitation technique was used for the synthesis of Ag@ZnO core-shell nanoparticles. The characteristics of the synthesized material were established using physical techniques. The material remained stable even at 400 °C. Disinfection efficiency of the Ag@ZnO core-shell nanoparticles was confirmed in the case of real world samples of pond, river, municipal tap water and was found to be better than that of pure ZnO and TiO₂ (Degussa P25). When the nanoparticle- based catalyst was recycled and reused for subsequent disinfection experiments, its efficiency did not change remarkably, even after three cycles. The sonochemically synthesized Ag@ZnO core-shell nanoparticles thus have a good potential for application in solar photocatalytic disinfection of water borne pathogens.
Das, Sourav; Ranjana, Neha; Misra, Ananyo Jyoti; Suar, Mrutyunjay; Mishra, Amrita; Tripathy, Suraj K.
2017-01-01
Water borne pathogens present a threat to human health and their disinfection from water poses a challenge, prompting the search for newer methods and newer materials. Disinfection of the Gram-negative bacterium Escherichia coli and the Gram-positive coccal bacterium Staphylococcus aureus in an aqueous matrix was achieved within 60 and 90 min, respectively, at 35 °C using solar-photocatalysis mediated by sonochemically synthesized Ag@ZnO core-shell nanoparticles. The efficiency of the process increased with the increase in temperature and at 55 °C the disinfection for the two bacteria could be achieved in 45 and 60 min, respectively. A new ultrasound-assisted chemical precipitation technique was used for the synthesis of Ag@ZnO core-shell nanoparticles. The characteristics of the synthesized material were established using physical techniques. The material remained stable even at 400 °C. Disinfection efficiency of the Ag@ZnO core-shell nanoparticles was confirmed in the case of real world samples of pond, river, municipal tap water and was found to be better than that of pure ZnO and TiO2 (Degussa P25). When the nanoparticle- based catalyst was recycled and reused for subsequent disinfection experiments, its efficiency did not change remarkably, even after three cycles. The sonochemically synthesized Ag@ZnO core-shell nanoparticles thus have a good potential for application in solar photocatalytic disinfection of water borne pathogens. PMID:28698514
PEO-b-P4VP/Yttrium Hydroxide Hybrid Nanotubes as Supporter for Catalyst Gold Nanoparticles
NASA Astrophysics Data System (ADS)
Yang, Qian; Chen, Dao-yong
2012-06-01
The adsorption of poly (ethylene oxide)-b-poly(4-vinylpyridine)(PEO-b-P4VP) micelles onto the surface of yttrium hydroxide nanotubes (YNTs) resulted in the hybrid nanotubes with a dense P4VP inner layer and a stretched PEO outer layer surrounding YNTs. The dense P4VP layer was further stabilized by the crosslinking using 1,4-dibromobutane as the crosslinker. Then, the crosslinked hybrid nanotubes (CHNTs) were used as a novel nano supporter for loading the catalyst gold nanoparticles (GNPs) within the crosslinked P4VP layer. The resultant GNPs/CHNTs (GNTs loaded on CHNTs) were applied to catalyze the reduction reaction of p-nitrophenol. The results indicate that this novel nano supporter has advantages such as good dispersity in the suspension, high capacity in loading GNPs (0.87 mmol/g), high catalytic activity of the loaded GNPs (12.9 μmol-1min-1), and good reusability of GNTs/CHNTs.
Freestanding films of crosslinked gold nanoparticles prepared via layer-by-layer spin-coating.
Schlicke, Hendrik; Schröder, Jan H; Trebbin, Martin; Petrov, Alexey; Ijeh, Michael; Weller, Horst; Vossmeyer, Tobias
2011-07-29
A new, extremely efficient method for the fabrication of films comprised of gold nanoparticles (GNPs) crosslinked by organic dithiols is presented in this paper. The method is based on layer-by-layer spin-coating of both components, GNPs and crosslinker, and enables the deposition of films several tens of nanometers in thickness within a few minutes. X-ray diffraction and conductance measurements reveal the proper adjustment concentration of the crosslinker solution of the critical is in order to prevent the destabilization and coalescence of particles. UV/vis spectroscopy, atomic force microscopy, and conductivity measurements indicate that films prepared via layer-by-layer spin-coating are of comparable quality to coatings prepared via laborious layer-by-layer self-assembly using immersion baths. Because spin-coated films are not bound chemically to the substrate, they can be lifted-off by alkaline underetching and transferred onto 3d-electrodes to produce electrically addressable, freely suspended films. Comparative measurements of the sheet resistances indicate that the transfer process does not compromise the film quality.
Freestanding films of crosslinked gold nanoparticles prepared via layer-by-layer spin-coating
NASA Astrophysics Data System (ADS)
Schlicke, Hendrik; Schröder, Jan H.; Trebbin, Martin; Petrov, Alexey; Ijeh, Michael; Weller, Horst; Vossmeyer, Tobias
2011-07-01
A new, extremely efficient method for the fabrication of films comprised of gold nanoparticles (GNPs) crosslinked by organic dithiols is presented in this paper. The method is based on layer-by-layer spin-coating of both components, GNPs and crosslinker, and enables the deposition of films several tens of nanometers in thickness within a few minutes. X-ray diffraction and conductance measurements reveal the proper adjustment concentration of the crosslinker solution of the critical is in order to prevent the destabilization and coalescence of particles. UV/vis spectroscopy, atomic force microscopy, and conductivity measurements indicate that films prepared via layer-by-layer spin-coating are of comparable quality to coatings prepared via laborious layer-by-layer self-assembly using immersion baths. Because spin-coated films are not bound chemically to the substrate, they can be lifted-off by alkaline underetching and transferred onto 3d-electrodes to produce electrically addressable, freely suspended films. Comparative measurements of the sheet resistances indicate that the transfer process does not compromise the film quality.
NASA Astrophysics Data System (ADS)
Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria
2017-12-01
We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required.
Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria
2017-01-01
Abstract We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required. PMID:28804527
Ryan, Catherine; Alcock, Emma; Buttimer, Finbarr; Schmidt, Michael; Clarke, David; Pemble, Martyn; Bardosova, Maria
2017-01-01
We present a study of a range of cross-linked chitosan composites with potential antimicrobial applications. They were formed by cross-linking chitosan and siloxane networks and by introducing silver and gold nanoparticles (NPs). The aim was to investigate whether adding the metal NPs to the chitosan-siloxane composite would lead to a material with enhanced antimicrobial ability as compared to chitosan itself. The composites were synthesised in hydrogel form with the metal NPs embedded in the cross-linked chitosan network. Spectroscopic and microscopic techniques were employed to investigate the structural properties of the composite and the tensile strength of the structures was measured. It was found that the addition of metal NPs did not influence the mechanical strength of the composite. A crystal violet attachment assay results displayed a significant reduction in the attachment of E. coli to the cross-linked chitosan surfaces. Release profile tests suggest that the metal NPs do not contribute to the overall antimicrobial activity under neutral conditions. The contribution to the mechanical and antimicrobial properties from cross-linking with siloxane is significant, giving rise to a versatile, durable, antimicrobial material suitable for thin film formation, wound dressings or the coating of various surfaces where robustness and antimicrobial control are required.
Synthesis of NiAu alloy and core-shell nanoparticles in water-in-oil microemulsions
NASA Astrophysics Data System (ADS)
Chiu, Hsin-Kai; Chiang, I.-Chen; Chen, Dong-Hwang
2009-07-01
NiAu alloy nanoparticles with various Ni/Au molar ratios were synthesized by the hydrazine reduction of nickel chloride and hydrogen tetrachloroaurate in the microemulsion system. They had a face-centered cubic structure and a mean diameter of 6-13 nm, decreasing with increasing Au content. As Au nanoparticles did, they showed a characteristic absorption peak at about 520 nm but the intensity decreased with increasing Ni content. Also, they were nearly superparamagnetic, although the magnetization decreased significantly with increasing Au content. Under an external magnetic field, they could be self-organized into the parallel lines. In addition, the core-shell nanoparticles, Ni3Au1@Au, were prepared by the Au coating on the surface of Ni3Au1 alloy nanoparticles. By increasing the hydrogen tetrachloroaurate concentration for Au coating, the thickness of Au shells could be raised and led to an enhanced and red-shifted surface plasmon absorption.
Onesto, V; Villani, M; Coluccio, M L; Majewska, R; Alabastri, A; Battista, E; Schirato, A; Calestani, D; Coppedé, N; Cesarelli, M; Amato, F; Di Fabrizio, E; Gentile, F
2018-04-10
Diatom shells are a natural, theoretically unlimited material composed of silicon dioxide, with regular patterns of pores penetrating through their surface. For their characteristics, diatom shells show promise to be used as low cost, highly efficient drug carriers, sensor devices or other micro-devices. Here, we demonstrate diatom shells functionalized with gold nanoparticles for the harvesting and detection of biological analytes (bovine serum albumin-BSA) and chemical pollutants (mineral oil) in low abundance ranges, for applications in bioengineering, medicine, safety, and pollution monitoring.
Dutta, Moumita; Prasankumar, Rohit Prativadi; Natarajan, Kamaraju; ...
2017-08-07
Magnetoelastoelectric coupling in an engineered biphasic multiferroic nanocomposite enables a novel magnetic field direction-defined propagation control of terahertz (THz) waves. These core–shell nanoparticles are comprised of a ferromagnetic cobalt ferrite core and a ferroelectric barium titanate shell. Furthermore, an assembly of these nanoparticles, when operated in external magnetic fields, exhibits a controllable amplitude modulation when the magnetic field is applied antiparallel to the THz wave propagation direction; yet the same assembly displays an additional phase modulation when the magnetic field is applied along the propagation direction. And while field-induced magnetostriction of the core leads to amplitude modulation, phase modulation ismore » a result of stress-mediated piezoelectricity of the outer ferroelectric shell.« less
NASA Astrophysics Data System (ADS)
Song, Lu; Wang, Yafei; Ma, Jing; Zhang, Qinghua; Shen, Zhijian
2018-06-01
Zinc oxide (ZnO) is a competitive candidate in semiconductor photocatalysts, only if the efficiency could be fully optimized especially by tailored nanostructures. Here we report a kind of core/shell structured Zn/ZnO nanoparticles with enhanced photocatalysis efficiency, which were synthesized by a highly-productive gaseous laser ablation method. The nanodroplets generated by laser ablation would be reduced to zinc in the protective atmosphere, and further be oxidized at surface to form a specific core/shell structured Zn/ZnO nanoparticles within seconds. Thanks to the formation of this Zn-ZnO Schottky junction, the photocatalysis degradation efficiency of such core/shell Zn/ZnO nanostructure is significantly improved owing to the enhanced visible light absorption and inhibited carrier recombination by introducing the metallic zinc.
Low-power upconversion in dye-doped polymer nanoparticles.
Simon, Yoan C; Bai, Shuo; Sing, Michelle K; Dietsch, Hervé; Achermann, Marc; Weder, Christoph
2012-04-13
Examples of nanoscale low-power upconverting systems are rapidly increasing because of their potential application in numerous areas such as bioimaging or drug delivery. The fabrication of dye-doped cross-linked rubbery nanoparticles that exhibit upconversion even at relatively low power densities is reported here. The nanoparticles were prepared by surfactant-free emulsion polymerization of n-butylacrylate with divinylbenzene as a cross-linker, followed by dyeing of the resulting particles with a two-chromophore system composed of a palladium porphyrin sensitizer, and diphenylanthracene. Blue emission (≈440 nm) of these systems was observed upon excitation at 532 nm. In addition to their optical properties, the particles were characterized by electron microscopy and dynamic light scattering. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wu, Zexing; Wang, Jie; Han, Lili
2016-01-19
Investigating active, stable, and low-cost materials for the oxygen reduction reaction is one of the key challenges in fuel-cell research. In this work, we describe the formation of N-doped carbon shell coated Co@CoO nanoparticles supported on Vulcan XC-72 carbon materials (Co@CoO@N–C/C) based on a simple supramolecular gel-assisted method. The double-shelled Co@CoO@N–C/C core–shell nanoparticles exhibit superior electrocatalytic activities for the oxygen reduction reaction compared to N-doped carbon and cobalt oxides, demonstrating the synergistic effect of the hybrid nanomaterials. Notably, the Co@CoO@N–C/C nanoparticles give rise to a comparable four-electron selectivity, long-term stability, and high methanol tolerance; all show a multi-fold improvement overmore » the commercial Pt/C catalyst. As a result, the progress is of great importance in exploring advanced non-precious metal-based electrocatalysts for fuel cell applications.« less
Yang, Jianping; Wang, Yunxiao; Li, Wei; Wang, Lianjun; Fan, Yuchi; Jiang, Wan; Luo, Wei; Wang, Yang; Kong, Biao; Selomulya, Cordelia; Liu, Hua Kun; Dou, Shi Xue; Zhao, Dongyuan
2017-12-01
Smart surface coatings of silicon (Si) nanoparticles are shown to be good examples for dramatically improving the cyclability of lithium-ion batteries. Most coating materials, however, face significant challenges, including a low initial Coulombic efficiency, tedious processing, and safety assessment. In this study, a facile sol-gel strategy is demonstrated to synthesize commercial Si nanoparticles encapsulated by amorphous titanium oxide (TiO 2 ), with core-shell structures, which show greatly superior electrochemical performance and high-safety lithium storage. The amorphous TiO 2 shell (≈3 nm) shows elastic behavior during lithium discharging and charging processes, maintaining high structural integrity. Interestingly, it is found that the amorphous TiO 2 shells offer superior buffering properties compared to crystalline TiO 2 layers for unprecedented cycling stability. Moreover, accelerating rate calorimetry testing reveals that the TiO 2 -encapsulated Si nanoparticles are safer than conventional carbon-coated Si-based anodes. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Das, D.; Hussain, A. M. P.
2018-04-01
PbS/CdS core/shell (CS) nanoparticles (NPs) were fabricated with three different concentrations of PbS core and CdS shell. Formation of core/shell heterostructure was confirmed from X-ray diffraction studies. The diffraction patterns exhibited formation of cubic phase and polycrystalline core/shell nanostructure. The crystalline sizes calculated from Williamson-Hall plot exhibited increase with molar concentration of precursors with decrease in strain. High resolution electron microscopy studies also confirm the formation of core/shell structure with particle size around 10 nm. A large blue-shift for PbS core compared to its bulk and small red-shift for the PbS/CdS core/shell as compared to the core is being observed in absorption spectra.
Zhang, Rui; Zhou, Tingting; Wang, Lili; Zhang, Tong
2018-03-21
Highly sensitive and stable gas sensors have attracted much attention because they are the key to innovations in the fields of environment, health, energy savings and security, etc. Sensing materials, which influence the practical sensing performance, are the crucial parts for gas sensors. Metal-organic frameworks (MOFs) are considered as alluring sensing materials for gas sensors because of the possession of high specific surface area, unique morphology, abundant metal sites, and functional linkers. Herein, four kinds of porous hierarchical Co 3 O 4 structures have been selectively controlled by optimizing the thermal decomposition (temperature, rate, and atmosphere) using ZIF-67 as precursor that was obtained from coprecipitation method with the co-assistance of cobalt salt and 2-methylimidazole in the solution of methanol. These hierarchical Co 3 O 4 structures, with controllable cross-linked channels, meso-/micropores, and adjustable surface area, are efficient catalytic materials for gas sensing. Benefits from structural advantages, core-shell, and porous core-shell Co 3 O 4 exhibit enhanced sensing performance compared to those of porous popcorn and nanoparticle Co 3 O 4 to acetone gas. These novel MOF-templated Co 3 O 4 hierarchical structures are so fantastic that they can be expected to be efficient sensing materials for development of low-temperature operating gas sensors.
Su, Xiaomeng; Li, Xiaoyan; Li, Junjie; Liu, Min; Lei, Fuhou; Tan, Xuecai; Li, Pengfei; Luo, Weiqiang
2015-03-15
Core-shell magnetic molecularly imprinted polymers (MIPs) nanoparticles (NPs), in which a Rhodamine B-imprinted layer was coated on Fe3O4 NPs. were synthesized. First, Fe3O4 NPs were prepared by a coprecipitation method. Then, amino-modified Fe3O4 NPs (Fe3O4@SiO2-NH2) was prepared. Finally, the MIPs were coated on the Fe3O4@SiO2-NH2 surface by the copolymerization with functional monomer, acrylamide, using a cross-linking agent, ethylene glycol dimethacrylate; an initiator, azobisisobutyronitrile and a template molecule, Rhodamine B. The Fe3O4@MIPs were characterized using a scanning electron microscope, Fourier transform infrared spectrometer, vibrating sample magnetometer, and re-binding experiments. The Fe3O4@MIPs showed a fast adsorption equilibrium, a highly improved imprinting capacity, and significant selectivity; they could be used as a solid-phase extraction material and detect illegal addition Rhodamine B in food. A method was developed for the selective isolation and enrichment of Rhodamine B in food samples with recoveries in the range 78.47-101.6% and the relative standard deviation was <2%. Copyright © 2014 Elsevier Ltd. All rights reserved.
Jain, Navin; Bhargava, Arpit; Rathi, Mohit; Dilip, R. Venkataramana; Panwar, Jitendra
2015-01-01
The present study demonstrates an economical and environmental affable approach for the synthesis of “protein-capped” silver nanoparticles in aqueous solvent system. A variety of standard techniques viz. UV-visible spectroscopy, transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and X-ray diffraction (XRD) measurements were employed to characterize the shape, size and composition of nanoparticles. The synthesized nanoparticles were found to be homogenous, spherical, mono-dispersed and covered with multi-layered protein shell. In order to prepare bare silver nanoparticles, the protein shell was removed from biogenic nanoparticles as confirmed by UV-visible spectroscopy, FTIR and photoluminescence analysis. Subsequently, the antibacterial efficacy of protein-capped and bare silver nanoparticles was compared by bacterial growth rate and minimum inhibitory concentration assay. The results revealed that bare nanoparticles were more effective as compared to the protein-capped silver nanoparticles with varying antibacterial potential against the tested Gram positive and negative bacterial species. Mechanistic studies based on ROS generation and membrane damage suggested that protein-capped and bare silver nanoparticles demonstrate distinct mode of action. These findings were strengthened by the TEM imaging along with silver ion release measurements using inductively coupled plasma atomic emission spectroscopy (ICP-AES). In conclusion, our results illustrate that presence of protein shell on silver nanoparticles can decrease their bactericidal effects. These findings open new avenues for surface modifications of nanoparticles to modulate and enhance their functional properties. PMID:26226385
Supramolecular domains in mixed peptide self-assembled monolayers on gold nanoparticles.
Duchesne, Laurence; Wells, Geoff; Fernig, David G; Harris, Sarah A; Lévy, Raphaël
2008-09-01
Self-organization in mixed self-assembled monolayers of small molecules provides a route towards nanoparticles with complex molecular structures. Inspired by structural biology, a strategy based on chemical cross-linking is introduced to probe proximity between functional peptides embedded in a mixed self-assembled monolayer at the surface of a nanoparticle. The physical basis of the proximity measurement is a transition from intramolecular to intermolecular cross-linking as the functional peptides get closer. Experimental investigations of a binary peptide self-assembled monolayer show that this transition happens at an extremely low molar ratio of the functional versus matrix peptide. Molecular dynamics simulations of the peptide self-assembled monolayer are used to calculate the volume explored by the reactive groups. Comparison of the experimental results with a probabilistic model demonstrates that the peptides are not randomly distributed at the surface of the nanoparticle, but rather self-organize into supramolecular domains.
Li, Yuan; Chopra, Nitin
2015-05-21
Patterned growth of multilayer graphene shell encapsulated gold nanoparticles (GNPs) and their covalent linking with inorganic quantum dots are demonstrated. GNPs were grown using a xylene chemical vapor deposition process, where the surface oxidized gold nanoparticles catalyze the multilayer graphene shell growth in a single step process. The graphene shell encapsulating gold nanoparticles could be further functionalized with carboxylic groups, which were covalently linked to amine-terminated quantum dots resulting in GNP-quantum dot heterostructures. The compositions, morphologies, crystallinity, and surface functionalization of GNPs and their heterostructures with quantum dots were evaluated using microscopic, spectroscopic, and analytical methods. Furthermore, optical properties of the derived architectures were studied using both experimental methods and simulations. Finally, GNP-quantum dot heterostructures were studied for photocatalytic degradation of phenol.
USDA-ARS?s Scientific Manuscript database
Chitosan–tripolyphosphate nanoparticles have been extensively studied during the last decade because of their numerous applications. In this study, we describe conditions to optimize chitosan nanoparticles as potential nano-fillers in edible films. The ionic cross-linking between the cationic amino ...
Li, Qianjin; Kamra, Tripta; Ye, Lei
2016-03-04
Addition of crosslinked polymer nanoparticles into a solution of a 3-nitrophenylboronic acid-alizarin complex leads to significant enhancement of fluorescence emission. Using the nanoparticle-enhanced boronic acid-alizarin system has improved greatly the sensitivity and extended the dynamic range of separation-free fluorescence assays for carbohydrates.
Kim, Ju-Young; Shim, Sun-Bo; Shim, Jin-Kie
2004-12-31
Amphiphilic polyurethane (APU) nanoparticles were synthesized through crosslinking polymerization of nano-aggregates of urethane acrylate nonionomer (UAN). The efficiency of in situ extraction of sorbed phenanthrene from aquifer material was tested using soil columns and compared with that of surfactants such as Triton X-100, Brij 30, and Tween 80. The extraction efficiency of those washing materials strongly depended on their concentration, flow rate, and the degree of sorption within soil column. That is, the extraction efficiency increased with the decrease of flow rate and the degree of sorption and the increase of the concentration. Even though the surfactants are superior to APU nanoparticles at solubilizing phenanthrene, at the same flow rate (0.02 mL/min) and concentration (4000 mg/L), the effectiveness of in situ soil washing of APU nanoparticles was about two times higher than those of surfactants. This is because, at the lower flow rates, the degree of sorption of APU nanoparticles was lower than that of surfactants, owing to the chemically crosslinked nature of APU nanoparticles.
Kothapalli, Satya V V N; Daeichin, Verya; Mastik, Frits; Brodin, Lars Åke; Janerot-Sjoberg, Birgitta; Paradossi, Gaio; de Jong, Nico; Grishenkov, Dmitry
2015-03-01
This work describes the fracturing mechanism of air-filled microbubbles (MBs) encapsulated by a cross-linked poly(vinyl alcohol) (PVA) shell. The radial oscillation and fracturing events following the ultrasound exposure were visualized with an ultrahigh-speed camera, and backscattered timedomain signals were acquired with the acoustic setup specific for harmonic detection. No evidence of gas emerging from defects in the shell with the arrival of the first insonation burst was found. In optical recordings, more than one shell defect was noted, and the gas core was drained without any sign of air extrusion when several consecutive bursts of 1 MPa amplitude were applied. In acoustic tests, the backscattered peak-to-peak voltage gradually reached its maximum and exponentially decreased when the PVA-based MB suspension was exposed to approximately 20 consecutive bursts arriving at pulse repetition frequencies of 100 and 500 Hz. Taking into account that the PVA shell is porous and possibly contains large air pockets between the cross-linked PVA chains, the aforementioned acoustic behavior might be attributed to pumping gas from these pockets in combination with gas release from the core through shell defects. We refer to this fracturing mechanism as pumping-out behavior, and this behavior could have potential use for the local delivery of therapeutic gases, such as nitric oxide.
Zhang, Jianan; Wang, Kaixi; Xu, Qun; ...
2015-02-25
In order to well address the problems of large volume change and dissolution of Fe 3O 4 nanomaterials during Li + intercalation/extraction, herein we demonstrate a one-step in situ nanospace-confined pyrolysis strategy for robust yolk–shell nanospindles with very sufficient internal void space (VSIVS) for high-rate and long-term lithium ion batteries (LIBs), in which an Fe 3O 4@Fe 3C core@shell nanoparticle is well confined in the compartment of a hollow carbon nanospindle. This structure can not only introduce VSIVS to accommodate volume change of Fe 3O 4 but also afford a dual shell of Fe 3C and carbon to restrict Femore » 3O 4 dissolution, thus providing dual roles for greatly improving the capacity retention. Consequently, Fe 3O 4@Fe 3C–C yolk–shell nanospindles deliver a high reversible capacity of 1128.3 mAh g –1 at even 500 mA g –1, excellent high rate capacity (604.8 mAh g –1 at 2000 mA g –1), and prolonged cycling life (maintaining 1120.2 mAh g –1 at 500 mA g –1 for 100 cycles) for LIBs, which are much better than those of Fe 3O 4@C core@shell nanospindles and Fe 3O 4 nanoparticles. The present Fe 3O 4@Fe 3C–C yolk–shell nanospindles are the most efficient Fe 3O 4-based anode materials ever reported for LIBs.« less
Li, Ling; Choo, Eugene Shi Guang; Tang, Xiaosheng; Ding, Jun; Xue, Junmin
2009-02-28
Cage-like silica hollow spheres loaded with superparamagnetic iron oxide nanoparticles incorporated in their macroporous shells are synthesized in a facile manner through a one-step oil-in-diethylene glycol (DEG) microemulsion route.
pH dependent conjugation of Ibuprofen to PEGylated nanoparticles
NASA Astrophysics Data System (ADS)
Bharti, Shivani; Jain, Shikshita; Kaur, Gurvir; Gupta, Shikha; Tripathi, S. K.
2018-04-01
In this paper, Ibuprofen, a water insoluble drug was covalently attached to PEGylated nanoparticles. Firstly, Surface functionalization of water dispersed core/shell nanoparticles had been done using hydrophilic polymer PEG-diamine. Therefore, PEGylated nanoparticles contain NH2 groups over the surface of nanoparticles and can be used for the further attachment of biomolecules. Ibuprofen was covalently loaded on the PEGylated core/shell nanoparticles using carbodiimide reaction. The synthesis had been carried out under two different pH environments, as the solubility of Ibuprofen is pH dependent. The resultant samples were characterized using UV-Vis absorption and FT-IR spectroscopy. The results strongly suggest the successful chemical conjugation of Ibuprofen to PEGylated nanoparticles in aqueous media and they could be further used for drug delivery applications.
Alqahtani, Mohammed S; Islam, M Saiful; Podaralla, Satheesh; Kaushik, Radhey S; Reineke, Joshua; Woyengo, Tofuko; Perumal, Omathanu
2017-03-06
The study was aimed at systematically investigating the influence of shell composition on the particle size, stability, release, cell uptake, permeability, and in vivo gastrointestinal distribution of food protein based nanocarriers for oral delivery applications. Three different core-shell nanocarriers were prepared using food-grade biopolymers including zein-casein (ZC) nanoparticles, zein-lactoferrin (ZLF), nanoparticles and zein-PEG (ZPEG) micelles. Nile red was used as a model hydrophobic dye for in vitro studies. The nanocarriers had negative, positive, and neutral charge, respectively. All three nanocarriers had a particle size of less than 200 nm and a low polydispersity index. The nanoparticles were stable at gastrointestinal pH (2-9) and ionic strength (10-200 mM). The nanocarriers sustained the release of Nile red in simulated gastric and intestinal fluids. ZC nanoparticles showed the slowest release followed by ZLF nanoparticles and ZPEG micelles. The nanocarriers were taken up by endocytosis in Caco-2 cells. ZPEG micelles showed the highest cell uptake and transepithelial permeability followed by ZLF and ZC nanoparticles. ZPEG micelles also showed P-gp inhibitory activity. All three nanocarriers showed bioadhesive properties. Cy 5.5, a near IR dye, was used to study the in vivo biodistribution of the nanocarriers. The nanocarriers showed longer retention in the rat gastrointestinal tract compared to the free dye. Among the three formulations, ZC nanoparticles was retained the longest in the rat gastrointestinal tract (≥24 h). Overall, the outcomes from this study demonstrate the structure-function relationship of core-shell protein nanocarriers. The findings from this study can be used to develop food protein based oral drug delivery systems with specific functional attributes.
Kim, Jun-Hyun; Bryan, William W; Lee, T Randall
2008-10-07
This report describes the structural and optical properties of a series of spherical shell/core nanoparticles in which the shell is comprised of a thin layer of gold, silver, or gold-silver alloy, and the core is comprised of a monodispersed silica nanoparticle. The silica core particles were prepared using the Stöber method, functionalized with terminal amine groups, and then seeded with small gold nanoparticles (approximately 2 nm in diameter). The gold-seeded silica particles were coated with a layer of gold, silver, or gold-silver alloy via solution-phase reduction of an appropriate metal ion or mixture of metal ions. The size, morphology, and elemental composition of the composite nanoparticles were characterized by field emission scanning electron microscopy (FE-SEM), energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, thermal gravimetric analysis (TGA), dynamic light scattering (DLS), and transmission electron microscopy (TEM). The optical properties of the nanoparticles were analyzed by UV-vis spectroscopy, which showed strong absorptions ranging from 400 nm into the near-IR region, where the position of the plasmon band reflected not only the thickness of the metal shell, but also the nature of the metal comprising the shell. Importantly, the results demonstrate a new strategy for tuning the position of the plasmon resonance without having to vary the core diameter or the shell thickness.
Kanoujia, Jovita; Singh, Mahendra; Singh, Pooja; Saraf, Shubhini A
2016-12-01
The objective of this study was to demonstrate the therapeutic as well as biopolymer like characteristics of naturally occurring sericin protein for development of nanoparticulate system of atorvastatin (Atr) to improve therapeutic effect and to reduce toxicity. The sericin encapsulated atorvastatin nanoparticles (Seri-Atr NPs) were prepared by desolvation method utilizing genipin (Gn) as a natural and nontoxic crosslinker. The optimized NPs exhibited small particle size (166±0.30nm), high entrapment efficiency (91±0.69%) and uniform spherical shape with sustained release profile. Moreover, the results of pharmacokinetic studies indicated an increase in AUC0-∞ of NPs (1189.74±52.3hng/ml) compared with Atr (501.84±66hng/ml). The cellular uptake of NPs suggested an interaction of negatively charged particles with the cell surface and considerable reduction in systemic toxicity. Histopathology studies also demonstrated the therapeutic potential of sericin and cytocompatibility. Hence, genipin crosslinked sericin based nanoparticles represents a promising nanoplatform for improved therapeutic efficiency of Atr. Copyright © 2016 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Shaik, Firdoz; Zhang, Weiqing; Niu, Wenxin; Lu, Xianmao
2014-10-01
Ligand-free Au nanoparticles with controlled sizes are synthesized via a volume-confined method. In this synthesis, mesoporous hollow silica shells (mHSS) are used as nano-containers for the impregnation of HAuCl4 solution before they are separated from the bulk solution. With a simple heating process, the Au precursor confined within the cavity of the isolated hollow shells is converted into ligand-free Au nanoparticles. The size of the Au nanoparticles can be tuned precisely by loading HAuCl4 solution of different concentrations, or by using mHSS with different cavity volumes. The ligand-free Au nanoparticles demonstrate superior catalytic activity than sodium citrate-capped Au nanoparticles.
Kosinski, Aaron M.; Brugnano, Jamie L.; Seal, Brandon L.; Knight, Frances C.; Panitch, Alyssa
2012-01-01
Poly(lactic-co-glycolic acid) (PLGA) is a popular material used to prepare nanoparticles for drug delivery. However, PLGA nanoparticles lack desirable attributes including active targeting abilities, resistance to aggregation during lyophilization, and the ability to respond to dynamic environmental stimuli. To overcome these issues, we fabricated a nanoparticle consisting of a PLGA core encapsulated within a shell of poly(N-isopropylacrylamide). Dynamic light scattering and transmission electron microscope imaging were used to characterize the nanoparticles, while an MTT assay and ELISA suggested biocompatibility in THP1 cells. Finally, a collagen type II binding assay showed successful modification of these nanoparticles with an active targeting moiety. PMID:23507885
NASA Astrophysics Data System (ADS)
Yan, Hai-Bo; Zhang, Yu-Qing; Ma, Yong-Lei; Zhou, Li-Xia
2009-11-01
Silk fibroin derived from Bombyx mori is a biomacromolecular protein with outstanding biocompatibility. When it was dissolved in highly concentrated CaCl2 solution and then the mixture of the protein and salt was subjected to desalting treatments for long time in flowing water, the resulting liquid silk was water-soluble polypeptides with different molecular masses, ranging from 8 to 70 kDa. When the liquid silk was introduced rapidly into acetone, silk protein nanoparticles with a range of 40-120 nm in diameter could be obtained. The crystalline silk nanoparticles could be conjugated covalently with insulin alone with cross-linking reagent glutaraldehyde. In vitro properties of the insulin-silk fibroin nanoparticles (Ins-SFN) bioconjugates were determined by Enzyme-Linked Immunosorbent Assay (ELISA). The optimal conditions for the biosynthesis of Ins-SFN bioconjugates were investigated. The Ins-SFN constructs obtained by 8 h of covalent cross-linking with 0.7% cross-linking reagent and the proportion of insulin and SFN being 30 IU: 15 mg showed much higher recoveries (90-115%). When insulin was coupled covalently with silk nanoparticles, the resistance of the modified insulin to trypsin digestion and in vitro stability in human serum were greatly enhanced as compared with insulin alone. The results in human serum indicated that the half-life in vitro of the biosynthesized Ins-SFN derivatives was about 2.5 times more than that of native insulin. Therefore, the silk protein nanoparticles have the potential values for being studied and developed as a new bioconjugate for enzyme/polypeptide drug delivery system.
Energetics of the formation of Cu-Ag core–shell nanoparticles
Chandross, Michael
2014-10-06
Our work presents molecular dynamics and Monte Carlo simulations aimed at developing an understanding of the formation of core–shell Cu-Ag nanoparticles. The effects of surface and interfacial energies were considered and used to form a phenomenological model that calculates the energy gained upon the formation of a core–shell structure from two previously distinct, non-interacting nanoparticles. In most cases, the core–shell structure was found to be energetically favored. Specifically, the difference in energy as a function of the radii of the individual Cu and Ag particles was examined, with the assumption that a core–shell structure forms. In general, it was foundmore » that the energetic gain from forming such a structure increased with increasing size of the initial Ag particle. This result was interpreted as a result of the reduction in surface energy. Moreover, for two separate particles, both Cu and Ag contribute to the surface energy; however, for a core–shell structure, the only contribution to the surface energy is from the Ag shell and the Cu contribution is changed to a Cu–Ag interfacial energy, which is always smaller.« less
Hwang, Hyeyoun; Kwon, Taehyun; Kim, Ho Young; Park, Jongsik; Oh, Aram; Kim, Byeongyoon; Baik, Hionsuck; Joo, Sang Hoon; Lee, Kwangyeol
2018-01-01
The development of highly active electrocatalysts is crucial for the advancement of renewable energy conversion devices. The design of core-shell nanoparticle catalysts represents a promising approach to boost catalytic activity as well as save the use of expensive precious metals. Here, a simple, one-step synthetic route is reported to prepare hexagonal nanosandwich-shaped Ni@Ru core-shell nanoparticles (Ni@Ru HNS), in which Ru shell layers are overgrown in a regioselective manner on the top and bottom, and around the center section of a hexagonal Ni nanoplate core. Notably, the synthesis can be extended to NiCo@Ru core-shell nanoparticles with tunable core compositions (Ni 3 Co x @Ru HNS). Core-shell HNS structures show superior electrocatalytic activity for the oxygen evolution reaction (OER) to a commercial RuO 2 black catalyst, with their OER activity being dependent on their core compositions. The observed trend in OER activity is correlated to the population of Ru oxide (Ru 4+ ) species, which can be modulated by the core compositions. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
NASA Astrophysics Data System (ADS)
Vatansever, Erol
2017-05-01
By means of Monte Carlo simulation method with Metropolis algorithm, we elucidate the thermal and magnetic phase transition behaviors of a ferrimagnetic core/shell nanocubic system driven by a time dependent magnetic field. The particle core is composed of ferromagnetic spins, and it is surrounded by an antiferromagnetic shell. At the interface of the core/shell particle, we use antiferromagnetic spin-spin coupling. We simulate the nanoparticle using classical Heisenberg spins. After a detailed analysis, our Monte Carlo simulation results suggest that present system exhibits unusual and interesting magnetic behaviors. For example, at the relatively lower temperature regions, an increment in the amplitude of the external field destroys the antiferromagnetism in the shell part of the nanoparticle, leading to a ground state with ferromagnetic character. Moreover, particular attention has been dedicated to the hysteresis behaviors of the system. For the first time, we show that frequency dispersions can be categorized into three groups for a fixed temperature for finite core/shell systems, as in the case of the conventional bulk systems under the influence of an oscillating magnetic field.
NASA Astrophysics Data System (ADS)
Khaparde, Rohini A.; Acharya, Smita A.
2018-05-01
ZnS:Mn/ ZnS core/shell nanoparticles was prepared by two step synthesis method. In first step, oleic acid - coated Mn doped ZnS core nanoparticles were prepared which were charged through ligand exchange. Shell of ZnS NPs was finally deposited upon the surface of charged Mn doped ZnS core. Scanning electron microscopy (SEM) image exhibit morphological confirmation of ZnS:Mn/ZnS core/shell. As Nano ZnS are the most suitable candidates for photocatalyst that extensively involved in degradation and complete mineralization of various toxic organic pollutants owing to its high efficiency, strong oxidizing power, non-toxicity, high photochemical and biological stability, corrosive resistance and low cost. Photodegradation of malachite green is systematically investigated by adding different molar proportional of ZnS:Mn/ZnS core/shell in the dye. The rate of de-coloration of dye is detected by UV-VIS absorption spectroscopy. Efficient detoriation in the colour of dye is attributed to the core /shell morphology of the particles.
Sinha, Tanur; Ahmaruzzaman, M
2015-09-01
The common household material, egg shell of Anas platyrhynchos is utilized for the synthesis of Silver and Gold-Silver core shell nanoparticles using greener, environment friendly and economic way. The egg shell extracts were acting as a stabilizing and reducing agents. This method avoids the use of external reducing and stabilizing agents, templates and solvents. The effects of various reaction parameters, such as reaction temperature, concentration in the formation of nanoparticles have also been investigated. The compositional abundance of gelatin may be envisaged for the effective reductive as well as stabilizing potency. The mechanisms for the formation of NPs have also been presented. The synthesized Ag NPs formed were predominantly spherical in nature with an average size of particles in the range of 6-26 nm. While, Au-Ag core shell nanoparticles formed were spherical and oval shaped, within a narrow size spectrum of 9-18 nm. Both the Ag NPs Au-and Ag core shell nanoparticles showed characteristic Bragg's reflection planes of fcc structure and surface plasmon resonance at 430 nm and 365 nm, respectively. The NPs were utilized for the removal of toxic and hazardous dyes, such as Rose Bengal, Methyl Violet 6 B and Methylene Blue from aqueous phase. Approximately 98.2%, 98.4% and 97% degradations of Rose Bengal, Methyl Violet 6 B, and Methylene Blue were observed with Ag NPs, while the percentage degradation of these dyes was 97.3%, 97.6% and 96% with Au-Ag NPs, respectively. Therefore, the present study has opened up an innovative way for synthesizing Ag NPs and Au-Ag bimetallic nanostructures of different morphologies and sizes involving the utilization of egg shell extract. The high efficiency of the NPs as photocatalysts has opened a promising application for the removal of hazardous dyes from the industrial effluents. Copyright © 2015 Elsevier Inc. All rights reserved.
Core-Shell Composite Fibers for High-Performance Flexible Supercapacitor Electrodes.
Lu, Xiaoyan; Shen, Chen; Zhang, Zeyang; Barrios, Elizabeth; Zhai, Lei
2018-01-31
Core-shell nanofibers containing poly(acrylic acid) (PAA) and manganese oxide nanoparticles as the core and polypyrrole (PPy) as the shell were fabricated through electrospinning the solution of PAA and manganese ions (PAA/Mn 2+ ). The obtained nanofibers were stabilized by Fe 3+ through the interaction between Fe 3+ ions and carboxylate groups. Subsequent oxidation of Mn 2+ by KMnO 4 produced uniform manganese dioxide (MnO 2 ) nanoparticles in the fibers. A PPy shell was created on the fibers by immersing the fibers in a pyrrole solution where the Fe 3+ ions in the fiber polymerized the pyrrole on the fiber surfaces. In the MnO 2 @PAA/PPy core-shell composite fibers, MnO 2 nanoparticles function as high-capacity materials, while the PPy shell prevents the loss of MnO 2 during the charge/discharge process. Such a unique structure makes the composite fibers efficient electrode materials for supercapacitors. The gravimetric specific capacity of the MnO 2 @PAA/PPy core-shell composite fibers was 564 F/g based on cyclic voltammetry curves at 10 mV/s and 580 F/g based on galvanostatic charge/discharge studies at 5 A/g. The MnO 2 @PAA/PPy core-shell composite fibers also present stable cycling performance with 100% capacitance retention after 5000 cycles.
NASA Astrophysics Data System (ADS)
Zhang, Sideng; Sun, Bin; Jiang, Xiaoze; Li, Lili; Meng, Zhouqi; Zhu, Meifang
2015-01-01
We report a novel method to improve the anti-thermal-deformation performance of an ethylene-octene copolymer (POE) using vinyl functionalized silica nanoparticles (M-SiO2) as a sensitizer to enhance radiation-induced crosslinking. The M-SiO2 nanoparticles were prepared by coupling commercially available silica nanoparticles with KH570 (γ-methacryloxypropyl-trimethoxysilane, γ-MPS) and were blended with POE by melt blending. Then, the mixture was irradiated with γ-rays under a nitrogen atmosphere to form the crosslinked POE/M-SiO2 nanocomposite. The novel nanocomposites were characterized, and the results showed that the gel fraction was proportional to the content of M-SiO2 in the loading range studied in this work. When the content of M-SiO2 was 10 wt%, the gel fraction of POE was increased by approximately 50%, and the softening temperature (T0.5D) increased from 104.4 °C to 224.6 °C after a 120 kGy dose of radiation. The tensile strength of the POE/M-SiO2-10 nanocomposite was better than that of the neat POE copolymer irradiated with an absorption dose up to 100 kGy. In contrast, the elongation of the POE/M-SiO2-10 nanocomposite was lower than that of the neat POE irradiated under the same conditions, due to the increased degree of crosslinking by radiation. These results clearly demonstrated that the use of M-SiO2 as an irradiation sensitizer effectively enhanced the radiation-induced crosslinking of POE.
Mahmoud, Mahmoud A
2013-05-28
Enhancements of the Raman signal by the newly prepared gold-palladium and gold-platinum double-shell hollow nanoparticles were examined and compared with those using gold nanocages (AuNCs). The surface-enhanced Raman spectra (SERS) of thiophenol adsorbed on the surface of AuNCs assembled into a Langmuir-Blodgett monolayer were 10-fold stronger than AuNCs with an inner Pt or Pd shell. The chemical and electromagnetic enhancement mechanisms for these hollow nanoparticles were further proved by comparing the Raman enhancement of nitrothiophenol and nitrotoulene. Nitrothiophenol binds to the surface of the nanoparticles by covalent interaction, and Raman enhancement by both the two mechanisms is possible, while nitrotoulene does not form any chemical bond with the surface of the nanoparticles and hence no chemical enhancement is expected. Based on discrete dipole approximation (DDA) calculations and the experimental SERS results, AuNCs introduced a high electromagnetic enhancement, while the nanocages with inner Pt or Pd shell have a strong chemical enhancement. The optical measurements of the localized surface plasmon resonance (LSPR) of the nanocages with an outer Au shell and an inner Pt or Pd shell were found, experimentally and theoretically, to be broad compared with AuNCs. The possible reason could be due to the decrease of the coherence time of Au oscillated free electrons and fast damping of the plasmon energy. This agreed well with the fact that a Pt or Pd inner nanoshell decreases the electromagnetic field of the outer Au nanoshell while increasing the SERS chemical enhancement.
Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts
Garg, Aaron; Milina, Maria; Ball, Madelyn; ...
2017-05-25
Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. In conclusion, the ability to control shell coveragemore » and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.« less
Transition-Metal Nitride Core@Noble-Metal Shell Nanoparticles as Highly CO Tolerant Catalysts
DOE Office of Scientific and Technical Information (OSTI.GOV)
Garg, Aaron; Milina, Maria; Ball, Madelyn
Core–shell architectures offer an effective way to tune and enhance the properties of noble-metal catalysts. Herein, we demonstrate the synthesis of Pt shell on titanium tungsten nitride core nanoparticles (Pt/TiWN) by high temperature ammonia nitridation of a parent core–shell carbide material (Pt/TiWC). X-ray photoelectron spectroscopy revealed significant core-level shifts for Pt shells supported on TiWN cores, corresponding to increased stabilization of the Pt valence d-states. The modulation of the electronic structure of the Pt shell by the nitride core translated into enhanced CO tolerance during hydrogen electrooxidation in the presence of CO. In conclusion, the ability to control shell coveragemore » and vary the heterometallic composition of the shell and nitride core opens up attractive opportunities to synthesize a broad range of new materials with tunable catalytic properties.« less
Wen, Bao-Ying; Jin, Xi; Li, Yue; Wang, Ya-Hao; Li, Chao-Yu; Liang, Miao-Miao; Panneerselvam, Rajapandiyan; Xu, Qing-Chi; Wu, De-Yin; Yang, Zhi-Lin; Li, Jian-Feng; Tian, Zhong-Qun
2016-06-21
Correction for 'Shell-isolated nanoparticle-enhanced Raman spectroscopy study of the adsorption behaviour of DNA bases on Au(111) electrode surfaces' by Bao-Ying Wen et al., Analyst, 2016, DOI: 10.1039/c6an00180g.
Processes in suspensions of nanocomposite microcapsules exposed to external electric fields
NASA Astrophysics Data System (ADS)
Ermakov, A. V.; Lomova, M. V.; Kim, V. P.; Chumakov, A. S.; Gorbachev, I. A.; Gorin, D. A.; Glukhovskoy, E. G.
2016-04-01
Microcapsules with and without magnetite nanoparticles incorporated in the polyelectrolyte shell were prepared. The effect of external electric field on the nanocomposite polyelectrolyte microcapsules containing magnetite nanoparticles in the shell was studied in this work as a function of the electric field strength. Effect of electric fields on polyelectrolyte microcapsules and the control over integrity of polyelectrolyte microcapsules with and without inorganic nanoparticles by constant electric field has been investigated. Beads effect, aggregation and deformations of nanocomposite microcapsule shell in response to electric field were observed by confocal laser scanning microscopy (CLSM). Thus, a new approach for effect on the nanocomposite microcapsule, including opening microcapsule shell by an electric field, was demonstrated. These results can be used for creation of new systems for drug delivery systems with controllable release by external electric field.
Shahbazi, Mohammad-Ali; Almeida, Patrick Vingadas; Correia, Alexandra; Herranz-Blanco, Barbara; Shrestha, Neha; Mäkilä, Ermei; Salonen, Jarno; Hirvonen, Jouni; Santos, Hélder A
2017-03-10
Bioresponsive cytosolic nanobased multidelivery has been emerging as an enormously challenging novel concept due to the intrinsic protective barriers of the cells and hardly controllable performances of nanomaterials. Here, we present a new paradigm to advance nano-in-nano integration technology amenable to create multifunctional nanovehicles showing considerable promise to overcome restrictions of intracellular delivery, solve impediments of endosomal localization and aid effectual tracking of nanoparticles. A redox responsive intercalator chemistry comprised of cystine and 9-aminoacridine is designed as a cross-linker to cap carboxylated porous silicon nanoparticles with DNA. These intelligent nanocarriers are then encapsulated within novel one-pot electrostatically complexed nano-networks made of a zwitterionic amino acid (cysteine), an anionic bioadhesive polymer (poly(methyl vinyl ether-alt-maleic acid)) and a cationic endosomolytic polymer (polyethyleneimine). This combined nanocomposite is successfully tested for the co-delivery of hydrophobic (sorafenib) or hydrophilic (calcein) molecules loaded within the porous core, and an imaging agent covalently integrated into the polyplex shell by click chemistry. High loading capacity, low cyto- and hemo-toxicity, glutathione responsive on-command drug release, and superior cytosolic delivery are shown as achievable key features of the proposed formulation. Overall, formulating drug molecules, DNA and imaging agents, without any interference, in a physico-chemically optimized carrier may open a path towards broad applicability of these cost-effective multivalent nanocomposites for treating different diseases. Copyright © 2017 Elsevier B.V. All rights reserved.
Fabrication of Fe3O4@mSiO2 Core-Shell Composite Nanoparticles for Drug Delivery Applications
NASA Astrophysics Data System (ADS)
Uribe Madrid, Sergio I.; Pal, Umapada; Kang, Young Soo; Kim, Junghoon; Kwon, Hyungjin; Kim, Jungho
2015-05-01
We report the synthesis of Fe3O4@mSiO2 nanostructures of different meso-silica (mSiO2) shell thickness, their biocompatibility and behaviors for loading and release of a model drug ibuprofen. The composite nanostructures have superparamagnetic magnetite cores of 208 nm average size and meso-silica shells of 15 to 40 nm thickness. A modified Stöber method was used to grow the meso-silica shells over the hydrothermally grown monodispersed magnetite particles. The composite nanoparticles show very promising drug holding and releasing behaviors, which depend on the thickness of meso-silica shell. The biocompatibility of the meso-silica-coated and uncoated magnetite nanoparticles was tested through cytotoxicity assay on breast cancer (MCF-7), ovarian cancer (SKOV3), normal human lung fibroblasts MRC-5, and IMR-90 cells. The high drug holding capacity and reasonable biocompatibility of the nanostructures make them ideal agents for targeted drug delivery applications in human body.
NASA Astrophysics Data System (ADS)
Singh, N. Shanta; Ningthoujam, R. S.; Devi, L. Romila; Yaiphaba, N.; Sudarsan, V.; Singh, S. Dorendrajit; Vatsa, R. K.; Tewari, R.
2008-11-01
Nanoparticles of GdVO4 doped with Eu3+ and core/shell of GdVO4:Eu3+/GdVO4 are prepared by urea hydrolysis method using ethylene glycol as capping agent as well as reaction medium at 130 °C. Unit cell volume increases when GdVO4 is doped with Eu3+ indicating the substitution of Gd3+ lattice sites by Eu3+. From luminescence study, it is confirmed that there is no particle size effect on emission positions of Eu3+. Optimum luminescence intensity is found to be in 5-10 at. % Eu3+. Above these concentrations, luminescence intensity decreases due to concentration quenching effect. There is an enhancement in luminescence intensity of core/shell nanoparticles. This has been attributed to the reduction in surface inhomogenities of Eu3+ surroundings by bonding to GdVO4 shell. The lifetime for D50 level increases with annealing and core/shell formation.
Facile deposition of gold nanoparticles on core-shell Fe3O4@polydopamine as recyclable nanocatalyst
NASA Astrophysics Data System (ADS)
Zhao, Yan; Yeh, Yaowen; Liu, Rui; You, Jinmao; Qu, Fengli
2015-07-01
A simple and green method for the controllable synthesis of core-shell Fe3O4 polydopamine nanoparticles (Fe3O4@PDA NPs) with tunable shell thickness and their application as a recyclable nanocatalyst support is presented. Magnetite Fe3O4 NPs formed in a one-pot process by the hydrothermal approach with a diameter of ˜240 nm were coated with a polydopamine shell layer with a tunable thickness of 15-45 nm. The facile deposition of Au NPs atop Fe3O4@PDA NPs was achieved by utilizing PDA as both the reducing agent and the coupling agent. The satellite nanocatalysts exhibited high catalytic performance for the reduction of p-nitrophenol. Furthermore, the recovery and reuse of the catalyst was demonstrated 8 times without detectible loss in activity. The synergistic combination of unique features of PDA and magnetic nanoparticles establishes these core-shell NPs as a versatile platform for potential applications.
NASA Astrophysics Data System (ADS)
Mehn, Dora; Morasso, Carlo; Vanna, Renzo; Schiumarini, Domitilla; Bedoni, Marzia; Ciceri, Fabio; Gramatica, Furio
2014-03-01
The Wilms tumor gene (WT1) is a biomarker overexpressed in more than 90% of acute myeloid leukemia patients. Fast and sensitive detection of the WT1 in blood samples would allow monitoring of the minimal residual disease during clinical remission and would permit early detection of a potential relapse in acute myeloid leukemia. In this work, Surface Enhanced Raman Spectroscopy (SERS) based detection of the WT1 sequence using bifunctional, magnetic core - gold shell nanoparticles is presented. The classical co-precipitation method was applied to generate magnetic nanoparticles which were coated with a gold shell after modification with aminopropyltriethoxy silane and subsequent deposition of gold nanoparticle seeds. Simple hydroquinone based reduction procedure was applied for the shell growing in water based reaction mixture at room temperature. Thiolated ssDNA probes of the WT1 sequence were immobilized as capture oligonucleotides on the gold surface. Malachite green was applied both for testing the amplification performance of the core-shell colloidal SERS substrate and also as label dye of the target DNA sequence. The SERS enhancer efficacy of the core-shell nanomaterial was compared with the efficacy of classical spherical gold particles produced using the conventional citrate reduction method. The core-shell particles were found not only to provide an opportunity for facile separation in a heterogeneous reaction system but also to be superior regarding robustness as SERS enhancers.
NASA Astrophysics Data System (ADS)
Krajczewski, Jan; Abdulrahman, Heman Burhanalden; Kołątaj, Karol; Kudelski, Andrzej
2018-03-01
One tool that can be used for determining the structure and composition of surfaces of various materials (even in in situ conditions) is shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS). In SHINERS measurements, the surface under investigation is covered with a layer of surface-protected plasmonic nanoparticles, and then the Raman spectrum of the surface analysed is recorded. The plasmonic cores of the used core-shell structures act as electromagnetic nanoresonators, significantly locally enhancing the intensity of the electric field of the incident radiation, leading to a large increase in the efficiency of the generation of the Raman signal from molecules in the close proximity to the deposited SHINERS nanoresonators. A protective layer (from transparent dielectrics such as SiO2, Al2O3 or TiO2) prevents direct interaction between the plasmonic metal and the analysed surface (such interactions may lead to changes in the structure of the surface) and, in the case of plasmonic cores other than gold cores, the dielectric layer increases the chemical stability of the metal core. In this contribution, we show for the first time that core-shell nanoparticles having a silver core (both a solid and hollow one) and a shell of zirconium(IV) oxide are very efficient SHINERS nanoresonators that are significantly more stable in acidic and alkaline media than the silver-silica core-shell structures typically used for SHINERS experiments.
BaTiO3-core Au-shell nanoparticles for photothermal therapy and bimodal imaging.
Wang, Yanfei; Barhoumi, Aoune; Tong, Rong; Wang, Weiping; Ji, Tianjiao; Deng, Xiaoran; Li, Lele; Lyon, Sophie A; Reznor, Gally; Zurakowski, David; Kohane, Daniel S
2018-05-01
We report sub-100 nm metal-shell (Au) dielectric-core (BaTiO 3 ) nanoparticles with bimodal imaging abilities and enhanced photothermal effects. The nanoparticles efficiently absorb light in the near infrared range of the spectrum and convert it to heat to ablate tumors. Their BaTiO 3 core, a highly ordered non-centrosymmetric material, can be imaged by second harmonic generation, and their Au shell generates two-photon luminescence. The intrinsic dual imaging capability allows investigating the distribution of the nanoparticles in relation to the tumor vasculature morphology during photothermal ablation. Our design enabled in vivo real-time tracking of the BT-Au-NPs and observation of their thermally-induced effect on tumor vessels. Photothermal therapy induced by plasmonic nanoparticles has emerged as a promising approach to treating cancer. However, the study of the role of intratumoral nanoparticle distribution in mediating tumoricidal activity has been hampered by the lack of suitable imaging techniques. This work describes metal-shell (Au) dielectric-core (BaTiO 3 ) nanoparticles (abbreviated as BT-Au-NP) for photothermal therapy and bimodal imaging. We demonstrated that sub-100 nm BT-Au-NP can efficiently absorb near infrared light and convert it to heat to ablate tumors. The intrinsic dual imaging capability allowed us to investigate the distribution of the nanoparticles in relation to the tumor vasculature morphology during photothermal ablation, enabling in vivo real-time tracking of the BT-Au-NPs and observation of their thermally-induced effect on tumor vessels. Copyright © 2018 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Prado-Gotor, R; López-Pérez, G; Martín, M J; Cabrera-Escribano, F; Franconetti, A
2014-06-01
A systematic study of the interaction between free anionic gold nanoparticles and chitosan in a solution is presented. A spectroscopic study of the interaction between 10nm gold nanoparticles and low molecular weight chitosan is reported as a function of the concentration and pH of the polymer in a solution. Zeta potential measurements and TEM images indicate the effective aggregation of the nanoparticles in the presence of chitosan. At the same time, anionic gold nanoparticles act as crosslink agents to form chitosan nanocapsules with an average molecular size of 260nm. The changes of the surface plasmon band due to the adsorption of the polymer on the nanoparticle surface allow using of the citrate gold nanoparticles as sensors of the polymer for analytical purposes. The limit of detection for chitosan biopolymer is 69nM. The optimum pH for the interaction between the biopolymer and the nanoparticles is found at a value of 6.4, obtained from spectrophotometric measurements and applying a deconvolution analysis of the experimental data. A simple model based on molecular surface electrostatic interactions is proposed to understand the pH dependence of the investigated system. Copyright © 2014 Elsevier Inc. All rights reserved.
Graphene-bonded and -encapsulated si nanoparticles for lithium ion battery anodes.
Wen, Yang; Zhu, Yujie; Langrock, Alex; Manivannan, Ayyakkannu; Ehrman, Sheryl H; Wang, Chunsheng
2013-08-26
Silicon (Si) has been considered a very promising anode material for lithium ion batteries due to its high theoretical capacity. However, high-capacity Si nanoparticles usually suffer from low electronic conductivity, large volume change, and severe aggregation problems during lithiation and delithiation. In this paper, a unique nanostructured anode with Si nanoparticles bonded and wrapped by graphene is synthesized by a one-step aerosol spraying of surface-modified Si nanoparticles and graphene oxide suspension. The functional groups on the surface of Si nanoparticles (50-100 nm) not only react with graphene oxide and bind Si nanoparticles to the graphene oxide shell, but also prevent Si nanoparticles from aggregation, thus contributing to a uniform Si suspension. A homogeneous graphene-encapsulated Si nanoparticle morphology forms during the aerosol spraying process. The open-ended graphene shell with defects allows fast electrochemical lithiation/delithiation, and the void space inside the graphene shell accompanied by its strong mechanical strength can effectively accommodate the volume expansion of Si upon lithiation. The graphene shell provides good electronic conductivity for Si nanoparticles and prevents them from aggregating during charge/discharge cycles. The functionalized Si encapsulated by graphene sample exhibits a capacity of 2250 mAh g⁻¹ (based on the total mass of graphene and Si) at 0.1C and 1000 mAh g⁻¹ at 10C, and retains 85% of its initial capacity even after 120 charge/discharge cycles. The exceptional performance of graphene-encapsulated Si anodes combined with the scalable and one-step aerosol synthesis technique makes this material very promising for lithium ion batteries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Synthesis and thermal behavior of tin-based alloy (Sn-Ag-Cu) nanoparticles
NASA Astrophysics Data System (ADS)
Roshanghias, Ali; Yakymovych, Andriy; Bernardi, Johannes; Ipser, Herbert
2015-03-01
The prominent melting point depression of nanoparticles has been the subject of a considerable amount of research. For their promising applications in electronics, tin-based nano-alloys such as near-eutectic Sn-Ag-Cu (SAC) alloys have been synthesized via various techniques. However, due to issues such as particle aggregation and oxidation or introduced impurities, the application of these nano-size particles has been confined or aborted. For instance, thermal investigations by DTA/DSC in a large number of studies revealed exothermic peaks in the range of 240-500 °C, i.e. above the melting point of SAC nanoparticles, with different and quite controversial explanations for this unclear phenomenon. This represents a considerable drawback for the application of nanoparticles. Correspondingly, in the current study, the thermal stability of SAC nanoparticles has been investigated via electron microscopy, XRD, FTIR, and DSC/TG analysis. It was found that the nanoparticles consist mainly of a metallic β-Sn core and an amorphous tin hydroxide shell structure. The SnO crystalline phase formation from this amorphous shell has been associated with the exothermic peaks on the first heating cycle of the nanoparticles, followed by a disproportionation reaction into metallic Sn and SnO2.The results also revealed that the surfactant and reducing agent cannot only affect the size and size distribution of the nanoparticles, they might also alter the ratio between the amorphous shell and the crystalline core in the structure of particles.The prominent melting point depression of nanoparticles has been the subject of a considerable amount of research. For their promising applications in electronics, tin-based nano-alloys such as near-eutectic Sn-Ag-Cu (SAC) alloys have been synthesized via various techniques. However, due to issues such as particle aggregation and oxidation or introduced impurities, the application of these nano-size particles has been confined or aborted. For instance, thermal investigations by DTA/DSC in a large number of studies revealed exothermic peaks in the range of 240-500 °C, i.e. above the melting point of SAC nanoparticles, with different and quite controversial explanations for this unclear phenomenon. This represents a considerable drawback for the application of nanoparticles. Correspondingly, in the current study, the thermal stability of SAC nanoparticles has been investigated via electron microscopy, XRD, FTIR, and DSC/TG analysis. It was found that the nanoparticles consist mainly of a metallic β-Sn core and an amorphous tin hydroxide shell structure. The SnO crystalline phase formation from this amorphous shell has been associated with the exothermic peaks on the first heating cycle of the nanoparticles, followed by a disproportionation reaction into metallic Sn and SnO2.The results also revealed that the surfactant and reducing agent cannot only affect the size and size distribution of the nanoparticles, they might also alter the ratio between the amorphous shell and the crystalline core in the structure of particles. Dedicated to Prof. Brigitte Weiss.
Jimenez-Villar, Ernesto; Mestre, Valdeci; de Oliveira, Paulo C; de Sá, Gilberto F
2013-12-21
There has been growing interest in scattering media in recent years, due to their potential applications as solar collectors, photocatalyzers, random lasers and other novel optical devices. Here, we have introduced a novel core-shell scattering medium for a random laser composed of TiO2@Silica nanoparticles. Higher efficiency, lower laser threshold and long photobleaching lifetime in random lasers were demonstrated. This has introduced a new method or parameter (fraction of absorbed pumping), which opens a new avenue to characterize and study the scattering media. Optical chemical and colloidal stabilities were combined by coating a suitable silica shell onto TiO2 nanoparticles.
Rana, S; Rawat, J; Sorensson, M M; Misra, R D K
2006-07-01
The present study describes and makes a relative comparison of the antimicrobial function of undoped and neodymium-doped titania coated-nickel ferrite composite nanoparticles processed by uniquely combining the reverse micelle and chemical hydrolysis approaches. This methodology facilitates the formation of undoped and doped photocatalytic titania shells and a magnetic ferrite core. The ferrite core is needed to help in the removal of particles from the sprayed surface using a small magnetic field. Doping of the titania shell with neodymium significantly enhances the photocatalytic and anti-microbial function of the core-shell composite nanoparticles without influencing the magnetic characteristics of the nickel ferrite core. The increased performance is believed to be related to the inhibition of electron-hole recombination and a decrease in the band gap energy of titania. The retention of magnetic strength ensures controlled movement of the composite nanoparticles by the magnetic field, facilitating their application as removable anti-microbial photocatalyst nanoparticles. The consistent behavior of the composite nanoparticles points to the viability of the synthesis process adopted.
van der Meer, Selina Beatrice; Knuschke, Torben; Frede, Annika; Schulze, Nina; Westendorf, Astrid M; Epple, Matthias
2017-07-15
Avidin was covalently conjugated to the surface of calcium phosphate nanoparticles, coated with a thin silica shell and terminated by sulfhydryl groups (diameter of the solid core about 50nm), with a bifunctional crosslinker connecting the amino groups of avidin to the sulfhydryl group on the nanoparticle surface. This led to a versatile nanoparticle system where all kinds of biotinylated (bio-)molecules can be easily attached to the surface by the non-covalent avidin-biotin-complex formation. It also permits the attachment of different biomolecules on the same nanoparticle (heteroavidity), creating a modular system for specific applications in medicine and biology. The variability of the binding to the nanoparticle surface of the was demonstrated with various biotinylated molecules, i.e. fluorescent dyes and antibodies. The accessibility of the conjugated avidin was demonstrated by a fluorescence-quenching assay. About 2.6 binding sites for biotin were accessible on each avidin tetramer. Together with a number of about 240 avidin tetramer units per nanoparticle, this offers about 600 binding sites for biotin on each nanoparticle. The uptake of fluorescently labelled avidin-conjugated calcium phosphate nanoparticles by HeLa cells showed the co-localization of fluorescent avidin and fluorescent biotin, indicating the stability of the complex under cell culture conditions. CD11c-antibody functionalized nanoparticles specifically targeted antigen-presenting immune cells (dendritic cells; DCs) in vitro and in vivo (mice) with high efficiency. Calcium phosphate nanoparticles have turned out to be very useful transporters for biomolecules into cells, both in vitro and in vivo. However, their covalent surface functionalization with antibodies, fluorescent dyes, or proteins requires a separate chemical synthesis for each kind of surface molecule. We have therefore developed avidin-terminated calcium phosphate nanoparticles to which all kinds of biotinylated molecules can be easily attached, also as a mixture of two or more molecules. This non-covalent bond is stable both in cell culture and after injection into mice in vivo. Thus, we have created a highly versatile system for many applications, from the delivery of biomolecules over the targeting of cells and tissue to in vivo imaging. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Gold/silver core-shell 20 nm nanoparticles extracted from citrate solution examined by XPS
DOE Office of Scientific and Technical Information (OSTI.GOV)
Engelhard, Mark H.; Smith, Jordan N.; Baer, Donald R.
Silver nanoparticles of many types are widely used in consumer and medical products. The surface chemistry of particles and the coatings that form during synthesis or use in many types of media can significantly impact the behaviors of particles including dissolution, transformation and biological or environmental impact. Consequently it is useful to be able to extract information about the thickness of surface coatings and other attributes of nanoparticles produced in a variety of ways. It has been demonstrated that X-ray Photoelectron Spectroscopy (XPS) can be reliably used to determine the thickness of organic and other nanoparticles coatings and shells. However,more » care is required to produce reliable and consistent information. Here we report the XPS spectra from gold/silver core-shell nanoparticles of nominal size 20 nm removed from a citrate saturated solution after one and two washing cycles. The Simulation of Electron Spectra for Surface Analysis (SESSA) program had been used to model peak amplitudes to obtain information on citrate coatings that remain after washing and demonstrate the presence of the gold core. This data is provided so that others can compare use of SESSA or other modeling approaches to quantify the nature of coatings to those already published and to explore the impacts particle non-uniformities on XPS signals from core-shell nanoparticles.« less
NASA Astrophysics Data System (ADS)
Boyadjiev, Stefan I.; Santos, Gustavo dos Lopes; Szżcs, Júlia; Szilágyi, Imre M.
2016-03-01
In this study, monoclinic WO3 nanoparticles were obtained by thermal decomposition of (NH4)xWO3 in air at 600 °C. On them by atomic layer deposition (ALD) TiO2 films were deposited, and thus core/shell WO3/TiO2 nanocomposites were prepared. We prepared composites of WO3 nanoparticles with conductive polymer as PEDOT:PSS, and deposited thin films of them on glass and ITO substrates by spin coating. The formation, morphology, composition and structure of the as-prepared pure and composite nanoparticles, as well thin films, were studied by TEM, SEM-EDX and XRD. The photocatalytic activity of both the WO3 and core/shell WO3/TiO2 nanoparticles was studied by decomposing methyl orange in aqueous solution under UV light irradiation. Cyclic voltammetry measurements were performed on the composite PEDOT:PSS/WO3 thin films, and the coloring and bleaching states were studied.
Hernandez-Leon, Sergio G; Sarabia-Sainz, Jose Andre-I; Montfort, Gabriela Ramos-Clamont; Guzman-Partida, Ana M; Robles-Burgueño, Maria Del Refugio; Vazquez-Moreno, Luz
2017-10-12
Silica nanoparticles were functionalized with immobilized molecular bait, Cibacron Blue, and a porous polymeric bis-acrylamide shell. These nanoparticles represent a new alternative to capture low molecular weight (LMW) proteins/peptides, that might be potential biomarkers. Functionalized core-shell silica nanoparticles (FCSNP) presented a size distribution of 243.9 ± 11.6 nm and an estimated surface charge of -38.1 ± 0.9 mV. The successful attachment of compounds at every stage of synthesis was evidenced by ATR-FTIR. The capture of model peptides was determined by mass spectrometry, indicating that only the peptide with a long sequence of hydrophobic amino acids (alpha zein 34-mer) interacted with the molecular bait. FCSNP excluded the high molecular weight protein (HMW), BSA, and captured LMW proteins (myoglobin and aprotinin), as evidenced by SDS-PAGE. Functionalization of nanoparticles with Cibacron Blue was crucial to capture these molecules. FCSNP were stable after twelve months of storage and maintained a capacity of 3.1-3.4 µg/mg.
Core–Shell Au@Metal-Oxide Nanoparticle Electrocatalysts for Enhanced Oxygen Evolution
Strickler, Alaina L.; Escudero-Escribano, Marı́a; Jaramillo, Thomas F.
2017-09-25
Enhanced catalysis for electrochemical oxygen evolution is essential for the efficacy of many renewable energy technologies, including water electrolyzers and metal–air batteries. Recently, Au supports have been shown to enhance the activity of many 3d transition metal-oxide thin films for the oxygen evolution reaction (OER) in alkaline media. In this paper, we translate the beneficial impact of Au supports to high surface area, device-ready core–shell nanoparticles consisting of a Au-core and a metal-oxide shell (Au@M xO y where M = Ni, Co, Fe, and CoFe). Through a systematic evaluation, we establish trends in performance and illustrate the universal activity enhancementmore » when employing the Au-core in the 3d transition metal-oxide nanoparticles. Finally, the highest activity particles, Au@CoFeO x, demonstrate an overpotential of 328 ± 3 mV over a 2 h stability test at 10 mA cm –2, illustrating that strategically coupling Au support and mixed metal-oxide effects in a core–shell nanoparticle morphology is a promising avenue to achieve device-ready, high-performance OER catalysts.« less
Core–Shell Au@Metal-Oxide Nanoparticle Electrocatalysts for Enhanced Oxygen Evolution
DOE Office of Scientific and Technical Information (OSTI.GOV)
Strickler, Alaina L.; Escudero-Escribano, Marı́a; Jaramillo, Thomas F.
Enhanced catalysis for electrochemical oxygen evolution is essential for the efficacy of many renewable energy technologies, including water electrolyzers and metal–air batteries. Recently, Au supports have been shown to enhance the activity of many 3d transition metal-oxide thin films for the oxygen evolution reaction (OER) in alkaline media. In this paper, we translate the beneficial impact of Au supports to high surface area, device-ready core–shell nanoparticles consisting of a Au-core and a metal-oxide shell (Au@M xO y where M = Ni, Co, Fe, and CoFe). Through a systematic evaluation, we establish trends in performance and illustrate the universal activity enhancementmore » when employing the Au-core in the 3d transition metal-oxide nanoparticles. Finally, the highest activity particles, Au@CoFeO x, demonstrate an overpotential of 328 ± 3 mV over a 2 h stability test at 10 mA cm –2, illustrating that strategically coupling Au support and mixed metal-oxide effects in a core–shell nanoparticle morphology is a promising avenue to achieve device-ready, high-performance OER catalysts.« less
2014-05-10
based on modified fullerenes , carbon nanotubes and gold nanoparticles (including nanocages and nanorods) were very recently reported.4 Nevertheless, this...ratios of 1:1.6 and 1:16, in order to form an onion- like core-shell structure, containing TiN core and shells of TPP (inner shell) and chitosan (outer...These results nicely correlate with the cells viability results and the formation of the ROS is most likely the cause of the cells death (Figure 24
Bubble nucleation and migration in a lead-iron hydr(oxide) core-shell nanoparticle
Niu, Kaiyang; Frolov, Timofey; Xin, Huolin L.; ...
2015-10-05
Iron hydroxide is found in a wide range of contexts ranging from biominerals to steel corrosion, and it can transform to anhydrous oxide via releasing O 2 gas and H 2O. However, it is not well understood how gases transport through a crystal lattice. Here, we present in situ observation of the nucleation and migration of gas bubbles in iron (hydr)oxide using transmission electron microscopy. We create Pb–FeOOH model core–shell nanoparticles in a liquid cell. Under electron irradiation, iron hydroxide transforms to iron oxide, during which bubbles are generated, and they migrate through the shell to the nanoparticle surface. Geometricmore » phase analysis of the shell lattice shows an inhomogeneous stain field at the bubbles. In conclusion, our modeling suggests that the elastic interaction between the core and the bubble provides a driving force for bubble migration.« less
Bubble nucleation and migration in a lead–iron hydr(oxide) core–shell nanoparticle
Niu, Kaiyang; Frolov, Timofey; Xin, Huolin L.; Wang, Junling; Asta, Mark; Zheng, Haimei
2015-01-01
Iron hydroxide is found in a wide range of contexts ranging from biominerals to steel corrosion, and it can transform to anhydrous oxide via releasing O2 gas and H2O. However, it is not well understood how gases transport through a crystal lattice. Here, we present in situ observation of the nucleation and migration of gas bubbles in iron (hydr)oxide using transmission electron microscopy. We create Pb–FeOOH model core–shell nanoparticles in a liquid cell. Under electron irradiation, iron hydroxide transforms to iron oxide, during which bubbles are generated, and they migrate through the shell to the nanoparticle surface. Geometric phase analysis of the shell lattice shows an inhomogeneous stain field at the bubbles. Our modeling suggests that the elastic interaction between the core and the bubble provides a driving force for bubble migration. PMID:26438864
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Yung-Chen Andrew; Engelhard, Mark H.; Baer, Donald R.
2016-03-07
Abstract or short description: Spectral modeling of photoelectrons can serve as a valuable tool when combined with X-ray photoelectron spectroscopy (XPS) analysis. Herein, a new version of the NIST Simulation of Electron Spectra for Surface Analysis (SESSA 2.0) software, capable of directly simulating spherical multilayer NPs, was applied to model citrate stabilized Au/Ag-core/shell nanoparticles (NPs). The NPs were characterized using XPS and scanning transmission electron microscopy (STEM) to determine the composition and morphology of the NPs. The Au/Ag-core/shell NPs were observed to be polydispersed in size, non-circular, and contain off-centered Au-cores. Using the average NP dimensions determined from STEM analysis,more » SESSA spectral modeling indicated that washed Au/Ag-core shell NPs were stabilized with a 0.8 nm l« less
Lee, Yi-Hsuan; Wu, Hsi-Chin; Yeh, Chia-Wei; Kuan, Chen-Hsiang; Liao, Han-Tsung; Hsu, Horng-Chaung; Tsai, Jui-Che; Sun, Jui-Sheng; Wang, Tzu-Wei
2017-11-01
The development of osteochondral tissue engineering is an important issue for the treatment of traumatic injury or aging associated joint disease. However, the different compositions and mechanical properties of cartilage and subchondral bone show the complexity of this tissue interface, making it challenging for the design and fabrication of osteochondral graft substitute. In this study, a bilayer scaffold is developed to promote the regeneration of osteochondral tissue within a single integrated construct. It has the capacity to serve as a gene delivery platform to promote transfection of human mesenchymal stem cells (hMSCs) and the functional osteochondral tissues formation. For the subchondral bone layer, the bone matrix with organic (type I collagen, Col) and inorganic (hydroxyapatite, Hap) composite scaffold has been developed through mineralization of hydroxyapatite nanocrystals oriented growth on collagen fibrils. We also prepare multi-shell nanoparticles in different layers with a calcium phosphate core and DNA/calcium phosphate shells conjugated with polyethyleneimine to act as non-viral vectors for delivery of plasmid DNA encoding BMP2 and TGF-β3, respectively. Microbial transglutaminase is used as a cross-linking agent to crosslink the bilayer scaffold. The ability of this scaffold to act as a gene-activated matrix is demonstrated with successful transfection efficiency. The results show that the sustained release of plasmids from gene-activated matrix can promote prolonged transgene expression and stimulate hMSCs differentiation into osteogenic and chondrogenic lineages by spatial and temporal control within the bilayer composite scaffold. This improved delivery method may enhance the functionalized composite graft to accelerate healing process for osteochondral tissue regeneration. In this study, a gene-activated matrix (GAM) to promote the growth of both cartilage and subchondral bone within a single integrated construct is developed. It has the capacity to promote transfection of human mesenchymal stem cells (hMSCs) and the functional osteochondral tissues formation. The results show that the sustained release of plasmids including TGF-beta and BMP-2 from GAM could promote prolonged transgene expression and stimulate hMSCs differentiation into the osteogenic and chondrogenic lineages by spatial control manner. This improved delivery method should enhance the functionalized composite graft to accelerate healing process in vitro and in vivo for osteochondral tissue regeneration. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Nourbakhsh, Himan; Madadlou, Ashkan; Emam-Djomeh, Zahra; Wang, Yi-Cheng; Gunasekaran, Sundaram; Mousavi, Mohammad E
2016-02-24
A whey protein isolate solution was heat-denatured and treated with the enzyme transglutaminase, which cross-linked ≈26% of the amino groups and increased the magnitude of the ζ-potential value. The protein solution was microemulsified, and then the resulting water-in-oil microemulsion was dispersed within a gallic acid-rich model wastewater. Gallic acid extraction by the outlined microemulsion liquid membrane (MLM) from the exterior aqueous phase (wastewater) and accumulation within the internal aqueous nanodroplets induced protein cold-set gelation and resulted in the formation of gallic acid-enveloping nanoparticles. Measurements with a strain-controlled rheometer indicated a progressive increase in the MLM viscosity during gallic acid recovery corresponding to particle formation. The mean hydrodynamic size of the nanoparticles made from the heat-denatured and preheated enzymatically cross-linked proteins was 137 and 122 nm, respectively. The enzymatic cross-linking of whey proteins led to a higher gallic acid recovery yield and increased the glass transition enthalpy and temperature. A similar impact on glass transition indices was observed by the gallic acid-induced nanoparticulation of proteins. Scanning electron microscopy showed the existence of numerous jammed/fused nanoparticles. It was suggested on the basis of the results of Fourier transform infrared spectroscopy that the in situ nanoparticulation of proteins shifted the C-N stretching and C-H bending peaks to higher wavenumbers. X-ray diffraction results proposed a decreased β-sheet content for proteins because of the acid-induced particulation. The nanoparticles made from the enzymatically cross-linked protein were more stable against the in vitro gastrointestinal digestion and retained almost 19% of the entrapped gallic acid after 300 min sequential gastric and intestinal digestions.
Preparation and characterization of self-crosslinked organic/inorganic proton exchange membranes
NASA Astrophysics Data System (ADS)
Zhong, Shuangling; Cui, Xuejun; Dou, Sen; Liu, Wencong
A series of silicon-containing sulfonated polystyrene/acrylate (Si-sPS/A) nanoparticles are successfully synthesized via simple emulsion polymerization method. The Si-sPS/A latexes show good film-forming capability and the self-crosslinked organic/inorganic proton exchange membranes are prepared by pouring the Si-sPS/A nanoparticle latexes into glass plates and drying at 60 °C for 10 h and 120 °C for 2 h. The potential of the membranes in direct methanol fuel cells (DMFCs) is characterized preliminarily by studying their thermal stability, ion-exchange capacity, water uptake, methanol diffusion coefficient, proton conductivity and selectivity (proton conductivity/methanol diffusion coefficient). The results indicate that these membranes possess excellent thermal stability and methanol barrier due to the existence of self-crosslinked silica network. In addition, the proton conductivity of the membranes is in the range of 10 -3-10 -2 S cm -1 and all the membranes show much higher selectivity in comparison with Nafion ® 117. These results suggest that the self-crosslinked organic/inorganic proton exchange membranes are particularly promising in DMFC applications.
Timberman, Anthony; Yang, Rongfang; Papantones, Alex; Seitz, W. Rudolf
2018-01-01
A new type of biomimetic templated copolymer has been prepared by reverse addition fragmentation chain transfer polymerization (RAFT) in dioxane. The initial formulation includes the template fluorescein, N-isopropylacrylamide (NIPAM, 84 mol %), methacrylic acid (MAA, 5-mol %), 4-vinylpyridine (4-VP, 9 mmol %), and N,N′-methylenebis(acrylamide) (MBA, 2 mol %). PolyNIPAM is a thermosensitive polymer that comes out of aqueous solution above its lower critical solution temperature forming hydrophobic ‘crosslinks’. MAA and 4-VP interact in dioxane forming acid–base crosslinks. The excess 4-VP serves as a recognition monomer organizing around the template fluorescein to form a binding site that is held in place by the noncovalent and covalent crosslinks. The MBA is a covalent crosslinker. The RAFT agent in the resulting copolylmer was reduced to a thiol and attached to gold nanoparticles. The gold nanoparticle bound copolymer binds fluorescein completely in less than two seconds with an affinity constant greater than 108 M−1. A reference copolymer prepared with the same monomers by the same procedure binds fluorescein much more weakly. PMID:29693601
NASA Astrophysics Data System (ADS)
Zhang, Xianhong; Zhao, Sidi; Wang, Fang; Ma, Yuhong; Wang, Li; Chen, Dong; Zhao, Changwen; Yang, Wantai
2017-05-01
Polymer based dielectric composites were fabricated through incorporation of core-shell structured BaTiO3 (BT) nanoparticles into PVDF matrix by means of solution blending. Core-shell structured BT nanoparticles with different shell composition and shell thickness were prepared by grafting methacrylate monomer (MMA or TFEMA) onto the surface of BT nanoparticles via surface initiated atom transfer radical polymerization (SI-ATRP). The content of the grafted polymer and the micro-morphology of the core-shell structured BT nanoparticles were investigated by thermo gravimetric analyses (TGA) and transmission electron microscopy (TEM), respectively. The dielectric properties were measured by broadband dielectric spectroscopy. The results showed that high dielectric constant and low dielectric loss are successfully realized in the polymer based composites. Moreover, the type of the grafted polymer and its content had different effect on the dielectric constant. In detail, the attenuation of dielectric constant was 16.6% for BT@PMMA1/PVDF and 10.7% for BT@PMMA2/PVDF composite in the range of 10 Hz to 100 kHz, in which the grafted content of PMMA was 5.5% and 8.0%, respectively. However, the attenuation of dielectric constant was 5.5% for BT@PTFEMA1/PVDF and 4.0% for BT@PTFEMA2/PVDF composite, in which the grafted content of PTFEMA was 1.5% and 2.0%, respectively. These attractive features of BT@PTFEMA/PVDF composites suggested that dielectric ceramic fillers modified with fluorinated polymer can be used to prepare high performance composites, especially those with low dielectric loss and high dielectric constant.
Manikandan, V S; Palai, Akshaya K; Mohanty, Smita; Nayak, Sanjay K
2018-06-01
In the current investigation, TiO 2 and TiO 2 -ZnO (core-shell) spherical nanoparticles were synthesized by simple combined hydrolysis and refluxing method. A TiO 2 core nanomaterial on the shell material of ZnO was synthesized by utilizing variable ratios of ZnO. The structural characterization of TiO 2 -ZnO core/shell nanoparticles were done by XRD analysis. The spherical structured morphology of the TiO 2 -ZnO has been confirmed through field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) studies. The UV-visible spectra of TiO 2 -ZnO nanostructures were also compared with the pristine TiO 2 to investigate the shift of wavelength. The TiO 2 -ZnO core/shell nanoparticles at the interface efficiently collect the photogenarated electrons from ZnO and also ZnO act a barrier for reduced charge recombination of electrolyte and dye-nanoparticles interface. This combination improved the light absorption which induced the charge transfer ability and dye loading capacity of core-shell nanoparticles. An enhancement in the short circuit current (J sc ) from 1.67 mA/cm 2 to 2.1 mA/cm 2 has been observed for TiO 2 -ZnObased photoanode (with platinum free counter electrode), promises an improvement in the energy conversion efficiency by 57% in comparison with that of the DSSCs based on the pristine TiO 2 . Henceforth, TiO 2 -ZnO photoelectrode in ZnO will effectively act as barrier at the interface of TiO 2 -ZnO and TiO 2 , ensuring the potential for DSSC application. Copyright © 2018 Elsevier B.V. All rights reserved.
NASA Astrophysics Data System (ADS)
Xu, Xinhua; Lu, Ping; Guo, Meiqing; Fang, Mingzhong
2010-02-01
A composite coating which could control drug release and biocorrosion of magnesium alloy stent materials WE42 was prepared. This composite coating was fabricated on the surface of the micro-arc oxidation (MAO) film of the magnesium alloy, WE42, by mixing different degrees of cross-linked gelatin with well-dispersed poly( DL-lactide-co-glycolide) (PLGA) nanoparticles. The PLGA nanoparticles were prepared by emulsion solvent evaporation/extraction technique. Nano ZS laser diffraction particle size analyzer detected that the size of the nanoparticles to be 150-300 nm. Scanning electron microscopy (SEM) and atomic force microscopy (AFM) was used to analyze the morphology of the nanoparticles and the composite coating. Potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) were used to evaluate the corrosion behavior of the composite coating. Drug release was determined by ultraviolet-visible (UV-vis) spectrophotometer. The corrosion resistance of the composite coating was improved by preventing the corrosive ions from diffusing to the MAO films. The drug release rate of paclitaxel (PTX) exhibited a nearly linear sustained-release profile with no significant burst releases.
Fluorescent nanonetworks: A novel bioalley for collagen scaffolds and Tissue Engineering
Nidhin, Marimuthu; Vedhanayagam, Mohan; Sangeetha, Selvam; Kiran, Manikantan Syamala; Nazeer, Shaiju S.; Jayasree, Ramapurath S.; Sreeram, Kalarical Janardhanan; Nair, Balachandran Unni
2014-01-01
Native collagen is arranged in bundles of aligned fibrils to withstand in vivo mechanical loads. Reproducing such a process under in vitro conditions has not met with major success. Our approach has been to induce nanolinks, during the self-assembly process, leading to delayed rather than inhibited fibrillogenesis. For this, a designed synthesis of nanoparticles - using starch as a template and a reflux process, which would provide a highly anisotropic (star shaped) nanoparticle, with large surface area was adopted. Anisotropy associated decrease in Morin temperature and superparamagnetic behavior was observed. Polysaccharide on the nanoparticle surface provided aqueous stability and low cytotoxicity. Starch coated nanoparticles was utilized to build polysaccharide - collagen crosslinks, which supplemented natural crosslinks in collagen, without disturbing the conformation of collagen. The resulting fibrillar lamellae showed a striking resemblance to native lamellae, but had a melting and denaturation temperature higher than native collagen. The biocompatibility and superparamagnetism of the nanoparticles also come handy in the development of stable collagen constructs for various biomedical applications, including that of MRI contrast agents. PMID:25095810
Deng, Liandong; He, Xiaohua; Li, Aigui; Yang, Qiuxia; Dong, Anjie
2007-02-01
Poly(methacrylic acid-grafted-poly(ethylene glycol)) (P(MAA-g-EG)) hydrogel nanoparticles (HNPs) were prepared by a thermally-initiated free radical dispersion polymerization method. The effects of various reaction parameters on the preparation of HNPs were investigated, including the quantity of monomer, temperature, initiator dosage, crosslinker dosage, and co-stabilizer concentration. The reaction temperature at 75 degrees C was found to be suitable for preparing stable and small P(MAA-g-EG) HNPs. By adding a little amount of polyvinyl alcohol in the reaction media, P(MAA-g-EG) HNPs with narrow size distribution could be obtained. The effects of pH and the crosslinker dosage on the equilibrium swelling behavior of P(MAA-g-EG) HNPs were also studied. The P(MAA-g-EG) HNPs perform pH-responsive swelling behavior, which is strongly influenced by the crosslinker dosage.
Luo, Leilei; Liang, Yucang; Erichsen, Egil Severin; Anwander, Reiner
2018-05-17
A new class of hierarchically structured mesoporous silica core-shell nanoparticles (HSMSCSNs) with a periodic mesoporous organosilica (PMO) core and a mesoporous silica (MS) shell is reported. The applied one-pot, two-step strategy allows rational control over the core/shell chemical composition, topology, and pore/particle size, simply by adjusting the reaction conditions in the presence of cetyltrimethylammonium bromide (CTAB) as structure-directing agent under basic conditions. The spherical, ethylene- or methylene-bridged PMO cores feature hexagonal (p6mm) or cage-like cubic symmetry (Pm3‾ n) depending on the organosilica precursor. The hexagonal MS shell was obtained by n-hexane-induced controlled hydrolysis of TEOS followed by directional co-assembly/condensation of silicate/CTAB composites at the PMO cores. The HSMSCSNs feature a hierarchical pore structure with pore diameters of about 2.7 and 5.6 nm in the core and shell domains, respectively. The core sizes and shell thicknesses are adjustable in the ranges of 90-275 and 15-50 nm, respectively, and the surface areas (max. 1300 m 2 g -1 ) and pore volumes (max. 1.83 cm 3 g -1 ) are among the highest reported for core-shell nanoparticles. The adsorption and controlled release of the fungicide propiconazole by the HSMSCSNs showed a three-stage release profile. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.
Functionalized magnetic iron oxide/alginate core-shell nanoparticles for targeting hyperthermia
Liao, Shih-Hsiang; Liu, Chia-Hung; Bastakoti, Bishnu Prasad; Suzuki, Norihiro; Chang, Yung; Yamauchi, Yusuke; Lin, Feng-Huei; Wu, Kevin C-W
2015-01-01
Hyperthermia is one of the promising treatments for cancer therapy. However, the development of a magnetic fluid agent that can selectively target a tumor and efficiently elevate temperature while exhibiting excellent biocompatibility still remains challenging. Here a new core-shell nanostructure consisting of inorganic iron oxide (Fe3O4) nanoparticles as the core, organic alginate as the shell, and cell-targeting ligands (ie, D-galactosamine) decorated on the outer surface (denoted as Fe3O4@Alg-GA nanoparticles) was prepared using a combination of a pre-gel method and coprecipitation in aqueous solution. After treatment with an AC magnetic field, the results indicate that Fe3O4@Alg-GA nanoparticles had excellent hyperthermic efficacy in a human hepatocellular carcinoma cell line (HepG2) owing to enhanced cellular uptake, and show great potential as therapeutic agents for future in vivo drug delivery systems. PMID:26005343
Green Synthesis of Ag-Cu Nanoalloys Using Opuntia ficus- indica
NASA Astrophysics Data System (ADS)
Rocha-Rocha, O.; Cortez-Valadez, M.; Hernández-Martínez, A. R.; Gámez-Corrales, R.; Alvarez, Ramón A. B.; Britto-Hurtado, R.; Delgado-Beleño, Y.; Martinez-Nuñez, C. E.; Pérez-Rodríguez, A.; Arizpe-Chávez, H.; Flores-Acosta, M.
2017-02-01
Bimetallic Ag/Cu nanoparticles have been obtained by green synthesis using Opuntia ficus- indica plant extract. Two synthesis methods were applied to obtain nanoparticles with core-shell and Janus morphologies by reversing the order of precursors. Transmission electronic microscopy revealed size of 10 nm and 20 nm for the core-shell and Janus nanoparticles, respectively. Other small particles with size of up to 2 nm were also observed. Absorption bands attributed to surface plasmon resonance were detected at 440 nm and 500 nm for the core-shell and Janus nanoparticles, respectively. Density functional theory predicted a breathing mode type (BMT) located at low wavenumber due to small, low-energy clusters of (AgCu) n with n = 2 to 9, showing a certain correlation with the experimental one (at 220 cm-1). The dependence of the BMT on the number of atoms constituting the cluster is also studied.
Functionalized magnetic iron oxide/alginate core-shell nanoparticles for targeting hyperthermia.
Liao, Shih-Hsiang; Liu, Chia-Hung; Bastakoti, Bishnu Prasad; Suzuki, Norihiro; Chang, Yung; Yamauchi, Yusuke; Lin, Feng-Huei; Wu, Kevin C-W
2015-01-01
Hyperthermia is one of the promising treatments for cancer therapy. However, the development of a magnetic fluid agent that can selectively target a tumor and efficiently elevate temperature while exhibiting excellent biocompatibility still remains challenging. Here a new core-shell nanostructure consisting of inorganic iron oxide (Fe3O4) nanoparticles as the core, organic alginate as the shell, and cell-targeting ligands (ie, D-galactosamine) decorated on the outer surface (denoted as Fe3O4@Alg-GA nanoparticles) was prepared using a combination of a pre-gel method and coprecipitation in aqueous solution. After treatment with an AC magnetic field, the results indicate that Fe3O4@Alg-GA nanoparticles had excellent hyperthermic efficacy in a human hepatocellular carcinoma cell line (HepG2) owing to enhanced cellular uptake, and show great potential as therapeutic agents for future in vivo drug delivery systems.
NASA Astrophysics Data System (ADS)
Cristescu, R.; Popescu, C.; Socol, G.; Iordache, I.; Mihailescu, I. N.; Mihaiescu, D. E.; Grumezescu, A. M.; Balan, A.; Stamatin, I.; Chifiriuc, C.; Bleotu, C.; Saviuc, C.; Popa, M.; Chrisey, D. B.
2012-09-01
We report on thin film deposition of nanostructured Fe3O4/oleic acid/ceftriaxone and Fe3O4/oleic acid/cefepime nanoparticles (core/shell/adsorption-shell) were fabricated by matrix assisted pulsed laser evaporation (MAPLE) onto inert substrates. The thin films were characterized by profilometry, Fourier transform infrared spectroscopy, atomic force microscopy, and investigated by in vitro biological assays. The biological properties tested included the investigation of the microbial viability and the microbial adherence to the glass coverslip nanoparticle film, using Gram-negative and Gram-positive bacterial strains with known antibiotic susceptibility behavior, the microbial adherence to the HeLa cells monolayer grown on the nanoparticle pellicle, and the cytotoxicity on eukaryotic cells. The proposed system, based on MAPLE, could be used for the development of novel anti-microbial materials or strategies for fighting pathogenic biofilms frequently implicated in the etiology of biofilm associated chronic infections.
NASA Astrophysics Data System (ADS)
Robindro Singh, L.; Ningthoujam, R. S.; Sudarsan, V.; Srivastava, Iti; Dorendrajit Singh, S.; Dey, G. K.; Kulshreshtha, S. K.
2008-02-01
Nanoparticles of Eu3+ doped Y2O3 (core) and Eu3+ doped Y2O3 covered with Y2O3 shell (core-shell) are prepared by urea hydrolysis for 3 h in ethylene glycol medium at a relatively low temperature of 140 °C, followed by heating at 500 and 900 °C. Particle sizes determined from x-ray diffraction and transmission electron microscopic studies are 11 and 18 nm for 500 and 900 °C heated samples respectively. Based on the luminescence studies of 500 and 900 °C heated samples, it is confirmed that there is no particle size effect on the peak positions of Eu3+ emission, and optimum luminescence intensity is observed from the nanoparticles with a Eu3+ concentration of 4-5 at.%. A luminescence study establishes that the Eu3+ environment in amorphous Y (OH)3 is different from that in crystalline Y2O3. For a fixed concentration of Eu3+ doping, there is a reduction in Eu3+ emission intensity for core-shell nanoparticles compared to that of core nanoparticles, and this has been attributed to the concentration dilution effect. Energy transfer from the host to Eu3+ increases with increase of crystallinity.
Enhanced charge storage capability of Ge/GeO(2) core/shell nanostructure.
Yuan, C L; Lee, P S
2008-09-03
A Ge/GeO(2) core/shell nanostructure embedded in an Al(2)O(3) gate dielectrics matrix was produced. A larger memory window with good data retention was observed in the fabricated metal-insulator-semiconductor (MIS) capacitor for Ge/GeO(2) core/shell nanoparticles compared to Ge nanoparticles only, which is due to the high percentage of defects located on the surface and grain boundaries of the GeO(2) shell. We believe that the findings presented here provide physical insight and offer useful guidelines to controllably modify the charge storage properties of indirect semiconductors through defect engineering.
El-Toni, Ahmed Mohamed; Habila, Mohamed A; Labis, Joselito Puzon; ALOthman, Zeid A; Alhoshan, Mansour; Elzatahry, Ahmed A; Zhang, Fan
2016-02-07
With the evolution of nanoscience and nanotechnology, studies have been focused on manipulating nanoparticle properties through the control of their size, composition, and morphology. As nanomaterial research has progressed, the foremost focus has gradually shifted from synthesis, morphology control, and characterization of properties to the investigation of function and the utility of integrating these materials and chemical sciences with the physical, biological, and medical fields, which therefore necessitates the development of novel materials that are capable of performing multiple tasks and functions. The construction of multifunctional nanomaterials that integrate two or more functions into a single geometry has been achieved through the surface-coating technique, which created a new class of substances designated as core-shell nanoparticles. Core-shell materials have growing and expanding applications due to the multifunctionality that is achieved through the formation of multiple shells as well as the manipulation of core/shell materials. Moreover, core removal from core-shell-based structures offers excellent opportunities to construct multifunctional hollow core architectures that possess huge storage capacities, low densities, and tunable optical properties. Furthermore, the fabrication of nanomaterials that have the combined properties of a core-shell structure with that of a hollow one has resulted in the creation of a new and important class of substances, known as the rattle core-shell nanoparticles, or nanorattles. The design strategies of these new multifunctional nanostructures (core-shell, hollow core, and nanorattle) are discussed in the first part of this review. In the second part, different synthesis and fabrication approaches for multifunctional core-shell, hollow core-shell and rattle core-shell architectures are highlighted. Finally, in the last part of the article, the versatile and diverse applications of these nanoarchitectures in catalysis, energy storage, sensing, and biomedicine are presented.
De-alloyed platinum nanoparticles
Strasser, Peter [Houston, TX; Koh, Shirlaine [Houston, TX; Mani, Prasanna [Houston, TX; Ratndeep, Srivastava [Houston, TX
2011-08-09
A method of producing de-alloyed nanoparticles. In an embodiment, the method comprises admixing metal precursors, freeze-drying, annealing, and de-alloying the nanoparticles in situ. Further, in an embodiment de-alloyed nanoparticle formed by the method, wherein the nanoparticle further comprises a core-shell arrangement. The nanoparticle is suitable for electrocatalytic processes and devices.
Correlative cellular ptychography with functionalized nanoparticles at the Fe L-edge
DOE Office of Scientific and Technical Information (OSTI.GOV)
Gallagher-Jones, Marcus; Dias, Carlos Sato Baraldi; Pryor, Alan
Precise localization of nanoparticles within a cell is crucial to the understanding of cell-particle interactions and has broad applications in nanomedicine. Here in this paper, we report a proof-of-principle experiment for imaging individual functionalized nanoparticles within a mammalian cell by correlative microscopy. Using a chemically-fixed HeLa cell labeled with fluorescent core-shell nanoparticles as a model system, we implemented a graphene-oxide layer as a substrate to significantly reduce background scattering. We identified cellular features of interest by fluorescence microscopy, followed by scanning transmission X-ray tomography to localize the particles in 3D, and ptychographic coherent diffractive imaging of the fine features inmore » the region at high resolution. By tuning the X-ray energy to the Fe L-edge, we demonstrated sensitive detection of nanoparticles composed of a 22 nm magnetic Fe 3O 4 core encased by a 25-nm-thick fluorescent silica (SiO 2) shell. These fluorescent core-shell nanoparticles act as landmarks and offer clarity in a cellular context. Our correlative microscopy results confirmed a subset of particles to be fully internalized, and high-contrast ptychographic images showed two oxidation states of individual nanoparticles with a resolution of ~16.5 nm. The ability to precisely localize individual fluorescent nanoparticles within mammalian cells will expand our understanding of the structure/function relationships for functionalized nanoparticles.« less
Zyuzin, Mikhail V; Honold, Tobias; Carregal-Romero, Susana; Kantner, Karsten; Karg, Matthias; Parak, Wolfgang J
2016-04-06
The temperature-dependence of the hydrodynamic diameter and colloidal stability of gold-polymer core-shell particles with temperature-sensitive (poly(N-isopropylacrylamide)) and temperature-insensitive shells (polyallylaminine hydrochloride/polystyrensulfonate, poly(isobutylene-alt-maleic anhydride)-graft-dodecyl) are investigated in various aqueous media. The data demonstrate that for all nanoparticle agglomeration, i.e., increase in effective nanoparticle size, the presence of salts or proteins in the dispersion media has to be taken into account. Poly(N-isopropylacrylamide) coated nanoparticles show a reversible temperature-dependent increase in size above the volume phase transition of the polymer shell when they are dispersed in phosphate buffered saline or in media containing protein. In contrast, the nanoparticles coated with temperature-insensitive polymers show a time-dependent increase in size in phosphate buffered saline or in medium containing protein. This is due to time-dependent agglomeration, which is particularly strong in phosphate buffered saline, and induces a time-dependent, irreversible increase in the hydrodynamic diameter of the nanoparticles. This demonstrates that one has to distinguish between temperature- and time-induced agglomerations. Since the size of nanoparticles regulates their uptake by cells, temperature-dependent uptake of thermosensitive and non-thermosensitive nanoparticles by cells lines is compared. No temperature-specific difference between both types of nanoparticles could be observed. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Correlative cellular ptychography with functionalized nanoparticles at the Fe L-edge
Gallagher-Jones, Marcus; Dias, Carlos Sato Baraldi; Pryor, Alan; ...
2017-07-06
Precise localization of nanoparticles within a cell is crucial to the understanding of cell-particle interactions and has broad applications in nanomedicine. Here in this paper, we report a proof-of-principle experiment for imaging individual functionalized nanoparticles within a mammalian cell by correlative microscopy. Using a chemically-fixed HeLa cell labeled with fluorescent core-shell nanoparticles as a model system, we implemented a graphene-oxide layer as a substrate to significantly reduce background scattering. We identified cellular features of interest by fluorescence microscopy, followed by scanning transmission X-ray tomography to localize the particles in 3D, and ptychographic coherent diffractive imaging of the fine features inmore » the region at high resolution. By tuning the X-ray energy to the Fe L-edge, we demonstrated sensitive detection of nanoparticles composed of a 22 nm magnetic Fe 3O 4 core encased by a 25-nm-thick fluorescent silica (SiO 2) shell. These fluorescent core-shell nanoparticles act as landmarks and offer clarity in a cellular context. Our correlative microscopy results confirmed a subset of particles to be fully internalized, and high-contrast ptychographic images showed two oxidation states of individual nanoparticles with a resolution of ~16.5 nm. The ability to precisely localize individual fluorescent nanoparticles within mammalian cells will expand our understanding of the structure/function relationships for functionalized nanoparticles.« less
Binding Preferences of Amino Acids for Gold Nanoparticles: A Molecular Simulation Study.
Shao, Qing; Hall, Carol K
2016-08-09
A better understanding of the binding preference of amino acids for gold nanoparticles of different diameters could aid in the design of peptides that bind specifically to nanoparticles of a given diameter. Here we identify the binding preference of 19 natural amino acids for three gold nanoparticles with diameters of 1.0, 2.0, and 4.0 nm, and investigate the mechanisms that govern these preferences. We calculate potentials of mean force between 36 entities (19 amino acids and 17 side chains) and the three gold nanoparticles in explicit water using well-tempered metadynamics simulations. Comparing these potentials of mean force determines the amino acids' nanoparticle binding preferences and if these preferences are controlled by the backbone, the side chain, or both. Twelve amino acids prefer to bind to the 4.0 nm gold nanoparticle, and seven prefer to bind to the 2.0 nm one. We also use atomistic molecular dynamics simulations to investigate how water molecules near the nanoparticle influence the binding of the amino acids. The solvation shells of the larger nanoparticles have higher water densities than those of the smaller nanoparticles while the orientation distributions of the water molecules in the shells of all three nanoparticles are similar. The nanoparticle preferences of the amino acids depend on whether their binding free energy is determined mainly by their ability to replace or to reorient water molecules in the nanoparticle solvation shell. The amino acids whose binding free energy depends mainly on the replacement of water molecules are likely to prefer to bind to the largest nanoparticle and tend to have relatively simple side chain structures. Those whose binding free energy depends mainly on their ability to reorient water molecules prefer a smaller nanoparticle and tend to have more complex side chain structures.
Magnetically separable polymer (Mag-MIP) for selective analysis of biotin in food samples.
Uzuriaga-Sánchez, Rosario Josefina; Khan, Sabir; Wong, Ademar; Picasso, Gino; Pividori, Maria Isabel; Sotomayor, Maria Del Pilar Taboada
2016-01-01
This work presents an efficient method for the preparation of magnetic nanoparticles modified with molecularly imprinted polymers (Mag-MIP) through core-shell method for the determination of biotin in milk food samples. The functional monomer acrylic acid was selected from molecular modeling, EGDMA was used as cross-linking monomer and AIBN as radical initiator. The Mag-MIP and Mag-NIP were characterized by FTIR, magnetic hysteresis, XRD, SEM and N2-sorption measurements. The capacity of Mag-MIP for biotin adsorption, its kinetics and selectivity were studied in detail. The adsorption data was well described by Freundlich isotherm model with adsorption equilibrium constant (KF) of 1.46 mL g(-1). The selectivity experiments revealed that prepared Mag-MIP had higher selectivity toward biotin compared to other molecules with different chemical structure. The material was successfully applied for the determination of biotin in diverse milk samples using HPLC for quantification of the analyte, obtaining the mean value of 87.4% recovery. Copyright © 2015 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Liu, Shuqin; Chen, Darui; Zheng, Juan; Zeng, Lewei; Jiang, Jijun; Jiang, Ruifeng; Zhu, Fang; Shen, Yong; Wu, Dingcai; Ouyang, Gangfeng
2015-10-01
This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the adsorption of nonpolar organic pollutants by means of solid-phase microextraction (SPME). Owing to its high hydrophobicity, diverse pore size distribution and highly conjugated structure, a 10 μm HCP coating exhibited excellent adsorption abilities towards benzene-ring-containing polycyclic aromatic hydrocarbons (PAHs) and benzene series compounds (benzene, toluene, ethylbenzene and o-xylene; abbreviated to BTEX) and to highly hydrophobic long-chain n-alkanes. Finally, the HCP-nanoparticles-coated SPME fiber was applied to the simultaneous analysis of five PAHs in environmental water samples and satisfactory recoveries were achieved. The findings could provide a new benchmark for the exploitation of superb HCPs as effective adsorbents for SPME or other adsorption applications.This study presents the preparation and characterization of a nanoscale Davankov-type hyper-crosslinked-polymer (HCP) as an adsorbent of benzene-ring-containing dyes and organic pollutants. HCP nanoparticles post-crosslinked from a poly(DVB-co-VBC) precursor were synthesized in this study, possessing ultrahigh surface area, hydrophobicity and stability. The as-synthesized Davankov-type HCP exhibited a rapid and selective adsorption ability towards the benzene-ring-containing dyes due to its highly conjugated structure. Besides, for the first time, the prepared HCP nanoparticles were adopted for the adsorption of nonpolar organic pollutants by means of solid-phase microextraction (SPME). Owing to its high hydrophobicity, diverse pore size distribution and highly conjugated structure, a 10 μm HCP coating exhibited excellent adsorption abilities towards benzene-ring-containing polycyclic aromatic hydrocarbons (PAHs) and benzene series compounds (benzene, toluene, ethylbenzene and o-xylene; abbreviated to BTEX) and to highly hydrophobic long-chain n-alkanes. Finally, the HCP-nanoparticles-coated SPME fiber was applied to the simultaneous analysis of five PAHs in environmental water samples and satisfactory recoveries were achieved. The findings could provide a new benchmark for the exploitation of superb HCPs as effective adsorbents for SPME or other adsorption applications. Electronic supplementary information (ESI) available: Fig. S1-S8, details of optimization of the SPME condition, Tables S1-S5. See DOI: 10.1039/c5nr04624f
Kumar Pramanik, Sumit; Losada-Pérez, Patricia; Reekmans, Gunter; Carleer, Robert; D’Olieslaeger, Marc; Vanderzande, Dirk; Adriaensens, Peter; Ethirajan, Anitha
2017-01-01
With recent advances in the field of diagnostics and theranostics, liposomal technology has secured a fortified position as a potential nanocarrier. Specifically, radiation/photo-sensitive liposomes containing photo-polymerizable cross-linking lipids are intriguing as they can impart the vesicles with highly interesting properties such as response to stimulus and improved shell stability. In this work, 1,2-bis(10,12-tricosadiynoyl)-sn-glycero-3-phosphoethanolamine (DTPE) is used as a photo-polymerizable lipid to form functional hybrid-liposomes as it can form intermolecular cross-linking through the diacetylenic groups. Hybrid-liposomes were formulated using mixtures of DTPE and saturated lipids of different chain lengths (dipalmitoylphosphatidylcholine (DPPC) and dimirystoilphosphatidylcholine (DMPC)) at different molar ratios. The physico-chemical characteristics of the liposomes has been studied before and after UV irradiation using a combination of techniques: DSC, QCM-D and solid-state NMR. The results signify the importance of a subtle modification in alkyl chain length on the phase behavior of the hybrid-liposomes and on the degree of crosslinking in the shell. PMID:28406235
Chen, Chih-Kuang; Lin, Wei-Jen; Hsia, Yu; Lo, Leu-Wei
2017-03-01
Well-defined poly(ethylene glycol)-b-allyl functional polylactide-b-polylactides (PEG-APLA-PLAs) are synthesized through sequential ring-opening polymerization. PEG-APLA-PLAs that have amphiphilic properties and reactive allyl side chains on their intermediate blocks are successfully transferred to core-shell interface cross-linked micelles (ICMs) by micellization and UV-initiated irradiation. ICMs have demonstrated enhanced colloidal stability in physiological-mimicking media. Hydrophobic molecules such as Nile Red or doxorubicin (Dox) are readily loaded into ICMs; the resulting drug-ICM formulations possess slow and sustained drug release profiles under physiological-mimicking conditions. ICMs exhibit negligible cytotoxicity in human uterine sarcoma cancer cells by using biodegradable aliphatic polyester as the hydrophobic segments. Relative to free Dox, Dox-loaded ICMs show a reduced cytotoxicity due to the late intracellular release of Dox from ICMs. Overall, ICMs represent a new type of biodegradable cross-linked micelle and can be employed as a promising platform for delivering a broad variety of hydrophobic drugs. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Mazloomi-Rezvani, Mahsa; Salami-Kalajahi, Mehdi; Roghani-Mamaqani, Hossein
2018-06-01
Different core-shell nanoparticles with Au as core and stimuli-responsive polymers such as poly(acrylic acid) (PAA), poly(methacrylic acid) (PMAA), poly(N-isopropylacrylamide) (PNIPAAm), poly(N,N'-methylenebis(acrylamide)) (PMBA), poly(2-hydroxyethyl methacrylate) (PHEMA) and poly((2-dimethylamino)ethyl methacrylate) (PDMAEMA) as shells were fabricated via inverse emulsion polymerization. Dynamic light scattering (DLS) was used to investigate particles sizes and particle size distributions and transmission electron microscopy (TEM) was applied to observe the core-shell structure of Au-polymer nanoparticles. Also, surface charge of all samples was studied by measurement of zeta potentials. Synthesized core-shell nanoparticles were utilized as nanocarriers of DOX as anti-cancer drug and drug release behaviors were investigated in dark room and under irradiation of near-infrared (NIR) light. Results showed that all core-shell samples have particle sizes less than 100 nm with narrow particle size distributions. Moreover, amount of drug loading decreased by increasing zeta potential. In dark room, lower pH resulted in higher cumulative drug release due to better solubility of DOX in acidic media. Also, NIR lighting on DOX-loaded samples led to increasing cumulative drug release significantly. However, DOX-loaded Au-PAA and Au-PMAA showed higher drug release at pH = 7.4 compared to 5.3 under NIR lighting. Copyright © 2018 Elsevier B.V. All rights reserved.
Kéri, Albert; Kálomista, Ildikó; Ungor, Ditta; Bélteki, Ádám; Csapó, Edit; Dékány, Imre; Prohaska, Thomas; Galbács, Gábor
2018-03-01
In this study, the information that can be obtained by combining normal and high resolution single particle ICP-MS (spICP-MS) measurements for spherical bimetallic nanoparticles (BNPs) was assessed. One commercial certified core-shell Au-Ag nanoparticle and three newly synthesized and fully characterized homogenous alloy Au-Ag nanoparticle batches of different composition were used in the experiments as BNP samples. By scrutinizing the high resolution spICP-MS signal time profiles, it was revealed that the width of the signal peak linearly correlates with the diameter of nanoparticles. It was also observed that the width of the peak for same-size nanoparticles is always significantly larger for Au than for Ag. It was also found that it can be reliably determined whether a BNP is of homogeneus alloy or core-shell structure and that, in the case of the latter, the core comprises of which element. We also assessed the performance of several ICP-MS based analytical methods in the analysis of the quantitative composition of bimetallic nanoparticles. Out of the three methods (normal resolution spICP-MS, direct NP nebulization with solution-mode ICP-MS, and solution-mode ICP-MS after the acid dissolution of the nanoparticles), the best accuracy and precision was achieved by spICP-MS. This method allows the determination of the composition with less than 10% relative inaccuracy and better than 3% precision. The analysis is fast and only requires the usual standard colloids for size calibration. Combining the results from both quantitative and structural analyses, the core diameter and shell thickness of core-shell particles can also be calculated. Copyright © 2017 Elsevier B.V. All rights reserved.
Nanoscale Assembly of Actuating Cilia-Mimetic
NASA Astrophysics Data System (ADS)
Baird, Lance; Breidenich, Jennifer; Land, Bruce; Hayes, Allen; Benkoski, Jason; Keng, Pei; Pyun, Jeffrey
2009-03-01
The cilium is among the smallest mechanical actuators found in nature. We have taken inspiration from this design to create magnetic nanochains, measuring approximately 1-5 μm long and 25 nm in diameter. Fabricated from the self-assembly of cobalt nanoparticles, these flexible filaments actuate in an oscillating magnetic field. The cobalt nanoparticles were functionalized with a polystyrene/benzaldehyde surface coating, thus allowing the particles to form imine bonds with one another in the presence of a diamine terminated polyethylene glycol. These imine bonds effectively cross-linked the particles and held the nanochains together in the absence of a magnetic field. Using design of experiments (DOE) to efficiently screen the effects of cobalt nanoparticle concentration, crosslinker concentration, and surface chemistry, we determined that the morphology of the final structures could be explained primarily by physical interactions (i.e. magnetic forces) rather than chemistry.
[Preparation of scopolamine hydrobromide nanoparticles-in-microsphere system].
Lü, Wei-ling; Hu, Jin-hong; Zhu, Quan-gang; Li, Feng-qian
2010-07-01
This study is to prepare scopolamine hydrobromide nanoparticles-in-microsphere system (SH-NiMS) and evaluate its drug release characteristics in vitro. SH nanoparticles were prepared by ionic crosslinking method with tripolyphosphate (TPP) as crosslinker and chitosan as carrier. Orthogonal design was used to optimize the formulation of SH nanoparticles, which took the property of encapsulation efficiency and drug loading as evaluation parameters. With HPMC as carrier, adjusted the parameters of spray drying technique and sprayed the SH nanoparticles in microspheres encaposulated by HPMC was formed and which is called nanoparticles-in-microsphere system (NiMS). SH-NiMS appearances were observed by SEM, structure was obsearved by FT-IR and the release characteristics in vitro were evaluated. The optimized formulation of SH nanoparticles was TPP/CS 1:3 (w/w), HPMC 0.3%, SH 0.2%. The solution peristaltic speed of the spray drying technique was adjusted to 15%, and the temperature of inlet was 110 degrees C. The encapsulation product yeild, drug loading and particle sizes of SH-NiMS were 94.2%, 20.4%, and 1256.5 nm, respectively. The appearances and the structure of SH-NiMS were good. The preparation method of SH-NiMS is stable and reliable to use, which provide a new way to develop new dosage form.
Jayabalan, M; Shalumon, K T; Mitha, M K; Ganesan, K; Epple, M
2010-03-01
The effect of hydroxyapatite (HAP) on the performance of nanocomposites of an unsaturated polyester, i.e., hydroxy-terminated high molecular weight poly(proplyene fumarate) (HT-PPFhm), was investigated. A thermoset nanocomposite was prepared with nanoparticles of calcined HAP (<100 nm, rod-like shape, filler content 30 wt.%), HT-PPFhm and N-vinyl pyrrolidone, dibenzoyl peroxide and N,N-dimethyl aniline. Two more nanocomposites were prepared with precipitated HAP nanoparticles (<100 nm rod-like shape) and commercially available HAP nanoparticles (<200 nm spherical shape), respectively. Calcined HAP nanoparticles resulted in very good crosslinking in the resin matrix with high crosslinking density and interfacial bonding with the polymer, owing to the rod-like shape of the nanoparticles; this gave improved biomechanical strength and modulus and also controlled degradation of the nanocomposite for scaffold formation. The tissue compatibility and osteocompatibility of the nanocomposite containing calcined HAP nanoparticles was evaluated. The tissue compatibility was studied by intramuscular implantation in a rabbit animal model for 3 months as per ISO standard 10993/6. The in vivo femoral bone repair was also carried out in the rabbit animal model as per ISO standard 10993/6. The nanocomposite containing calcined HAP nanoparticles is both biocompatible and osteocompatible. Copyright 2009 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
Fashina, Adedayo; Amuhaya, Edith; Nyokong, Tebello
2015-02-25
This work presents the synthesis and characterization of a new zinc phthalocyanine complex tetrasubstituted with 3-carboxyphenoxy in the peripheral position. The photophysical properties of the new complex are compared with those of phthalocyanines tetra substituted with 3-carboxyphenoxy or 4-carboxyphenoxy at non-peripheral positions. Three phthalocyanine complexes were encapsulated within silica matrix to form a core shell and the hybrid nanoparticles particles obtained were spherical and mono dispersed. When encapsulated within the silica shell nanoparticles, phthalocyanines showed improved triplet quantum yields and singlet oxygen quantum yields than surface grafted derivatives. The improvements observed could be attributed to the protection provided for the phthalocyanine complexes by the silica matrix. Copyright © 2014 Elsevier B.V. All rights reserved.
Zhang, Junshuai; Yao, Tongjie; Zhang, Hui; Zhang, Xiao; Wu, Jie
2016-11-10
In this manuscript, we have introduced a novel method to improve the catalytic activity of metal nanoparticles via optimizing the support structure. To this end, raspberry-like γ-Fe 2 O 3 /crackled nitrogen-doped carbon (CNC) capsules were prepared by a two-step method. Compared with traditional magnetic capsules, in γ-Fe 2 O 3 /CNC capsules, the γ-Fe 2 O 3 nanoparticles were embedded in a CNC shell; therefore, they neither occupied the anchoring sites for metal nanoparticles nor came into contact with them, which was beneficial for increasing the metal nanoparticle loading. Numerous tiny cracks appeared on the porous CNC shell, which effectively improved the mass diffusion and transport in catalytic reactions. Additionally, the coordination interaction could be generated between the precursor metal ions and doped-nitrogen atoms in the capsule shell. With the help of these structural merits, γ-Fe 2 O 3 /CNC capsules were ideal supports for Pd nanoparticles, because they were beneficial for improving the Pd loading, reducing the nanoparticle size, increasing their dispersity and maximizing the catalytic performance of Pd nanoparticles anchored on the inner shell surface. As expected, γ-Fe 2 O 3 /CNC@Pd catalysts exhibited a dramatically enhanced catalytic activity towards hydrophilic 4-nitrophenol and hydrophobic nitrobenzene. The reaction rate constant k was compared with recent work and the corresponding reference samples. Moreover, they could be easily recycled by using a magnet and reused without an obvious loss of catalytic activity.
NASA Astrophysics Data System (ADS)
Fei, Haojie; Yang, Chongyang; Bao, Hua; Wang, Gengchao
2014-11-01
Flexible all-solid-state supercapacitors (SCs) are fabricated using graphene/carbon black nanoparticle (GCB) film electrodes and cross-linked poly(vinyl alcohol)-H2SO4 porous gel electrolytes (gPVAP-H2SO4). The GCB composite films, with carbon black (CB) nanoparticles uniformly distributed in the graphene nanosheets, greatly improve the active surface areas and ion transportation of pristine graphene film. The porous structure of as-prepared gPVAP-H2SO4 membrane improves the equilibrium swelling ratio in electrolyte and provides interconnected ion transport channels. The chemical crosslinking solves the fluidity problem of PVA-H2SO4 gel electrolyte at high temperature. As-fabricated GCB//gPVAP(20)-H2SO4//GCB flexible SC displays an increased specific capacitance (144.5 F g-1 at 0.5 A g-1) and a higher specific capacitance retention (67.9% from 0.2 to 4 A g-1). More importantly, the flexible SC possesses good electrochemical performance at high temperature (capacitance retention of 78.3% after 1000 cycles at 70 °C).
Koukaras, Emmanuel N; Papadimitriou, Sofia A; Bikiaris, Dimitrios N; Froudakis, George E
2012-10-01
This work reports details pertaining to the formation of chitosan nanoparticles that we prepare by the ionic gelation method. The molecular interactions of the ionic cross-linking of chitosan with tripolyphosphate have been investigated and elucidated by means of all-electron density functional theory. Solvent effects have been taken into account using implicit models. We have identified primary-interaction ionic cross-linking configurations that we define as H-link, T-link, and M-link, and we have quantified the corresponding interaction energies. H-links, which display high interaction energies and are also spatially broadly accessible, are the most probable cross-linking configurations. At close range, proton transfer has been identified, with maximum interaction energies ranging from 12.3 up to 68.3 kcal/mol depending on the protonation of the tripolyphosphate polyanion and the relative coordination of chitosan with tripolyphosphate. On the basis of our results for the linking types (interaction energies and torsion bias), we propose a simple mechanism for their impact on the chitosan/TPP nanoparticle formation process. We introduce the β ratio, which is derived from the commonly used α ratio but is more fundamental since it additionally takes into account structural details of the oligomers.
NASA Astrophysics Data System (ADS)
Thrift, W. J.; Darvishzadeh-Varcheie, M.; Capolino, F.; Ragan, R.
2017-08-01
Colloidal self-assembly combined with templated surfaces holds the promise of fabricating large area devices in a low cost facile manner. This directed assembly approach improves the complexity of assemblies that can be achieved with self-assembly while maintaining advantages of molecular scale control. In this work, electrokinetic driving forces, i.e., electrohydrodynamic flow, are paired with chemical crosslinking between colloidal particles to form close-packed plasmonic metamolecules. This method addresses challenges of obtaining uniformity in nanostructure geometry and nanometer scale gap spacings in structures. Electrohydrodynamic flows yield robust driving forces between the template and nanoparticles as well as between nanoparticles on the surface promoting the assembly of close-packed metamolecules. Here, electron beam lithography defined Au pillars are used as seed structures that generate electrohydrodynamic flows. Chemical crosslinking between Au surfaces enables molecular control over gap spacings between nanoparticles and Au pillars. An as-fabricated structure is analyzed via full wave electromagnetic simulations and shown to produce large magnetic field enhancements on the order of 3.5 at optical frequencies. This novel method for directed self-assembly demonstrates the synergy between colloidal driving forces and chemical crosslinking for the fabrication of plasmonic metamolecules with unique electromagnetic properties.
Inphonlek, Supharat; Pimpha, Nuttaporn; Sunintaboon, Panya
2010-06-01
The core-shell nanoparticles possessing poly(methyl methacrylate) (PMMA) core coated with chitosan (CS), polyethyleneimine (PEI), and chitosan-mixed-polyethyleneimine (CS/PEI) shells were synthesized in this work. The emulsifier-free emulsion polymerization triggered by a redox initiating system from t-butylhydroperoxide (TBHP) and amine groups on CS and/or PEI was used as a synthetic method. In the CS/PEI systems, the amount of CS was kept constant (0.5g), while the amount of PEI was varied from 0.1 to 0.5g. The surface and physico-chemical properties of prepared nanoparticles were then examined. FTIR spectra indicated the presence of grafted PMMA on CS and/or PEI, and the weight fraction of incorporated PEI in the CS/PEI nanoparticles. All nanoparticles were spherical in shape with uniform size distribution illustrated by scanning electron microscopy (SEM). The introduction of PEI to CS nanoparticles yielded the higher monomer conversion, grafting efficiency, and grafting percentage compared with the CS nanoparticles. The size of CS/PEI nanoparticles was smaller than the original CS and PEI nanoparticles, and tended to decrease with increasing amount of PEI introduced. The introduction of PEI also brought the higher colloidal stability to the nanoparticles as indicated by zeta-potential measurement and isoelectric point analysis. The nanoparticles exhibited a promising antibacterial activity against Staphylococcus aureus and Escherichia coli. The nanoparticle-bacteria interaction was studied via SEM. The results suggested that they would be useful as effective antibacterial agents. Copyright 2010 Elsevier B.V. All rights reserved.
Wang, Lin; Liu, Li; Dong, Bingyang; Zhao, Hanying; Zhang, Mingming; Chen, Wenjuan; Hong, Yanhang
2017-05-01
A thermoresponsive polymer-protein biodynamer was prepared via the bioconjugation of an aliphatic aldehyde-functionalized copolymer to hydrazine-modified bovine serum albumin (BSA) through reversible pyridylhydrazone linkages. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis (SDS-PAGE) and size exclusion chromatography (SEC) results indicated that the pyridylhydrazone linkages cleaved in an intracellular-mimicking acidic milieu, thus leading to the release of BSA. The dynamic character of the protein biodynamer was demonstrated by exchange reactions with aldehyde-containing molecules. The biodynamer self-assembled into spherical micelles at a temperature above its lower critical solution temperature (LCST). Subsequently, BSA molecules within the hydrophilic coronae of the micelles were readily cross-linked via reaction with cystamine at 45°C, and multi-stimuli-responsive nanoparticles were generated. The biohybrid nanoparticles reversibly swelled and shrank as the cores of the nanoparticles were solvated below the LCST and desolvated above the LCST. The accessible reversibility of the pyridylhydrazone bonds imparts pH-responsive and dynamic characteristics to the nanoparticles. The nanoparticles displayed glutathione (GSH) responsiveness, and the synergistic effects of pH and GSH resulted in complete disintegration of the nanoparticles under the intracellular-mimicking acidic and reductive conditions. The nanoparticles were also enzyme-responsive and disintegrated rapidly in the presence of protease. In vitro cytotoxicity and cell uptake assays demonstrated that the nanoparticles were highly biocompatible and effectively internalized by HepG2 cells, which make them interesting candidates as vehicles for drug delivery application and biomimetic platforms to investigate the biological process in nature. In this research, we report the synthesis of a temperature and pH dual-responsive polymer-protein biodynamer through reversible pyridylhydrazone formation. The prepared biodynamer can offer a potential platform for intracellular protein delivery. The multi-stimuli-responsive biohybrid nanoparticles containing disulfide functionalities are constructed by cross-linking albumin coronae of the biodynamer micelles. With the combination of a thermoresponsive polymer, protein and reversible covalent bonds, the biohybrid nanoparticles are endowed with highly biocompatible, environmentally responsive and adaptive features. These nanoparticles present the ability to undergo changes in their constitution, hydrodynamic size and nanostructure in response to physical, chemical and biological stimuli, which make them interesting candidates as vehicles for drug delivery application and a biomimetic platform to investigate the biological process in nature. Copyright © 2017 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Min, Yu-Lin; Wan, Yong; Yu, Shu-Hong
2009-01-01
A facile method to synthesize novel Au@Y 2O 3:Eu 3+ hollow sub-microspheres encapsulated with moveable gold nanoparticle core and Y 2O 3:Eu 3+ as shell via two-step coating processes and a succeeding calcination process has been developed. Silica coating on citrate-stabilized gold nanoparticles with a size of 25 nm can be obtained through a slightly modified Stöber process. Gold particles coated with double shell silica and Eu doped Y(OH) 3 can be obtained by coating on the Au@SiO 2 spheres through simply adding Y(NO 3) 3, Eu(NO 3) 3 and an appropriate quantity of NH 3·H 2O. Au@Y 2O 3:Eu 3+ hollow sub-microspheres with moveable individual Au nanoparticle as core can be obtained after calcination of Au@Y 2O 3:Eu 3+ particles at 600 °C for 2 h. These new core-shell structures with encapsulated gold nanoparticles have combined optical properties of both the Au nanoparticles and the Y 2O 3:Eu 3+ phosphor materials which might have potential applications.
Jafari, T; Simchi, A; Khakpash, N
2010-05-01
Core-shell iron-gold (Fe@Au) nanoparticles were synthesized by a facile reverse micelle procedure and the effect of water to surfactant molar ratio (w) on the size, size distribution and magnetic properties of the nanoparticles was studied. MTT assay was utilized to evaluate the cell toxicity of the nanoparticles. To functionalize the particles for MRI imaging and targeted drug delivery, the particles were coated by polyglycerol through capping with thiol followed by polymerization of glycidol. The characteristics of the particles were examined by X-ray diffraction (XRD), transmission electron microscopy (TEM), vibrating sample magnetometer (VSM), UV-visible spectroscopy, and Fourier transform infrared spectroscopy (FT-IR). It was found that the size and size distribution of the nanoparticles increase by increasing the water to surfactant molar ratio (w). The particles were spherical in shape with a thin layer of gold. Complementary growth of the gold shell on the iron core was noticed. Meanwhile, two types of agglomeration including magnetic beads and magnetic colloidal nanocrystals clusters were observed dependent on the w-value. The magnetic measurement studies revealed the superparamagnetic behavior of the nanoparticles. MTT assay result indicated the synthesized nanoparticles are nontoxic that will be useful for biomedical applications. Copyright 2010 Elsevier Inc. All rights reserved.
Photoresponsive lipid-polymer hybrid nanoparticles for controlled doxorubicin release
NASA Astrophysics Data System (ADS)
Yao, Cuiping; Wu, Ming; Zhang, Cecheng; Lin, Xinyi; Wei, Zuwu; Zheng, Youshi; Zhang, Da; Zhang, Zhenxi; Liu, Xiaolong
2017-06-01
Currently, photoresponsive nanomaterials are particularly attractive due to their spatial and temporal controlled drug release abilities. In this work, we report a photoresponsive lipid-polymer hybrid nanoparticle for remote controlled delivery of anticancer drugs. This hybrid nanoparticle comprises three distinct functional components: (i) a poly(D,L-lactide-co-glycolide) (PLGA) core to encapsulate doxorubicin; (ii) a soybean lecithin monolayer at the interface of the core and shell to act as a molecular fence to prevent drug leakage; (iii) a photoresponsive polymeric shell with anti-biofouling properties to enhance nanoparticle stability, which could be detached from the nanoparticle to trigger the drug release via a decrease in the nanoparticle’s stability under light irradiation. In vitro results revealed that this core-shell nanoparticle had excellent light-controlled drug release behavior (76% release with light irradiation versus 10% release without light irradiation). The confocal microscopy and flow cytometry results also further demonstrated the light-controlled drug release behavior inside the cancer cells. Furthermore, a CCK8 assay demonstrated that light irradiation could significantly improve the efficiency of killing cancer cells. Meanwhile, whole-animal fluorescence imaging of a tumor-bearing mouse also confirmed that light irradiation could trigger drug release in vivo. Taken together, our data suggested that a hybrid nanoparticle could be a novel light controlled drug delivery system for cancer therapy.
Wang, Hui; Yu, Yi-Fei; Chen, Qian-Wang; Cheng, Kai
2011-01-21
This communication demonstrates superparamagnetic nanosized particles with a magnetic core and a porous carbon shell (thickness of 11 nm), which can remove 97% of Pb(2+) ions from an acidic aqueous solution at a Pb(2+) ion concentration of 100 mg L(-1). It is suggested that a weak electrostatic force of attraction between the heavy metal ions and the nanoparticles and the heavy metal ions adsorption on the mesopore carbon shell contribute most to the superior removal property.
Cu2O-directed in situ growth of Au nanoparticles inside HKUST-1 nanocages.
Liu, Yongxin; Liu, Ting; Tian, Long; Zhang, Linlin; Yao, Lili; Tan, Taixing; Xu, Jin; Han, Xiaohui; Liu, Dan; Wang, Cheng
2016-12-07
Controllable integration of metal nanoparticles (MNPs) and metal-organic frameworks (MOFs) is attracting considerable attention as the obtained composite materials always show synergistic effects in applications of catalysis, delivery, as well as sensing. Herein, a Cu 2 O-directed in situ growth strategy was developed to integrate Au nanoparticles and HKUST-1. In this strategy, Cu 2 O@HKUST-1 core-shell heterostructures, HKUST-1 nanocages, Cu 2 O@Au@HKUST-1 sandwich core-shell heterostructures and Au@HKUST-1 balls-in-cage heterostructures were successfully synthesized. Cu 2 O@HKUST-1 core-shell heterostructures were synthesized by soaking Cu 2 O nanocrystals in benzene-1,3,5-tricarboxylic acid solution. The well-defined Cu 2 O@HKUST-1 core-shell heterostructures were demonstrated to be dominated by the ratio of Cu 2+ cations to btc 3- ligands in solution during the period of HKUST-1 formation. Cu 2 O@Au@HKUST-1 sandwich core-shell or Au@HKUST-1 balls-in-cage heterostructures were obtained by impregnating HAuCl 4 into Cu 2 O@HKUST-1 core-shell heterostructures. Due to the porosity of HKUST-1 and reducibility of Cu 2 O, HAuCl 4 could pass through the HKUST-1 shell and be reduced by the Cu 2 O core in situ forming Au nanoparticles. Finally, CO oxidation reaction at high temperatures was carried out to assess the catalytic functionality of the obtained composite heterostructures. This strategy can circumvent some drawbacks of the existing approaches for integrating MNPs and MOFs, such as nonselective deposition of MNPs at the outer surface of the MOF matrices, extreme treatment conditions and additional surface modifications.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Zhu, Huiyuan; Jiang, Guangming; Zhang, Xu
We report the synthesis of core/shell face-centered tetragonal (fct)-FePd/Pd nanoparticles (NPs) via reductive annealing of core/shell Pd/Fe 3O 4 NPs followed by temperature-controlled Fe etching in acetic acid. Among three different kinds of core/shell FePd/Pd NPs studied (FePd core at similar to 8 nm and Pd shell at 0.27, 0.65, or 0.81 nm), the fct-FePd/Pd-0.65 NPs are the most efficient catalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO 4 with Pt-like activity and durability. This enhanced ORR catalysis arises from the desired Pd lattice compression in the 0.65 nm Pd shell induced by the fct-FePd core. Lastly,more » our study offers a general approach to enhance Pd catalysis in acid for ORB.« less
Zhu, Huiyuan; Jiang, Guangming; Zhang, Xu; ...
2015-10-04
We report the synthesis of core/shell face-centered tetragonal (fct)-FePd/Pd nanoparticles (NPs) via reductive annealing of core/shell Pd/Fe 3O 4 NPs followed by temperature-controlled Fe etching in acetic acid. Among three different kinds of core/shell FePd/Pd NPs studied (FePd core at similar to 8 nm and Pd shell at 0.27, 0.65, or 0.81 nm), the fct-FePd/Pd-0.65 NPs are the most efficient catalyst for the oxygen reduction reaction (ORR) in 0.1 M HClO 4 with Pt-like activity and durability. This enhanced ORR catalysis arises from the desired Pd lattice compression in the 0.65 nm Pd shell induced by the fct-FePd core. Lastly,more » our study offers a general approach to enhance Pd catalysis in acid for ORB.« less
Fabrication of polyacrylate core-shell nanoparticles via spray drying method
NASA Astrophysics Data System (ADS)
Chen, Pengpeng; Cheng, Zenghui; Chu, Fuxiang; Xu, Yuzhi; Wang, Chunpeng
2016-05-01
Fine polyacrylate particles are thought to be environmental plastisols for car industry. However, these particles are mainly dried through demulsification of the latexes, which is not reproducible and hard to be scaled up. In this work, a spray drying method had been applied to the plastisols-used acrylate latex. By adjusting the core/shell ratio, spray drying process of the latex was fully studied. Scanning electronic microscopy observation of the nanoparticles before and after spray drying indicated that the core-shell structures could be well preserved and particles were well separated by spray drying if the shell was thick enough. Otherwise, the particles fused into each other and core-shell structures were destroyed. Polyacrylate plastisols were developed using diisononylphthalate as a plasticizer, and plastigels were obtained after heat treatment of the sols. Results showed that the shell thickness also had a great influence on the storage stability of the plastisols and mechanical properties of the plastigels.
Kim, Wansun; Lee, Jae-Chul; Lee, Gi-Ja; Park, Hun-Kuk; Lee, Anbok; Choi, Samjin
2017-06-20
We introduce a label-free biosensing cellulose strip sensor with surface-enhanced Raman spectroscopy (SERS)-encoded bimetallic core@shell nanoparticles. Bimetallic nanoparticles consisting of a synthesis of core Ag nanoparticles (AgNP) and a synthesis of shell gold nanoparticles (AuNPs) were fabricated on a cellulose substrate by two-stage successive ionic layer absorption and reaction (SILAR) techniques. The bimetallic nanoparticle-enhanced localized surface plasmon resonance (LSPR) effects were theoretically verified by computational calculations with finite element models of optimized bimetallic nanoparticles interacting with an incident laser source. Well-dispersed raspberry-like bimetallic nanoparticles with highly polycrystalline structure were confirmed through X-ray and electron analyses despite ionic reaction synthesis. The stability against silver oxidation and high sensitivity with superior SERS enhancement factor (EF) of the low-cost SERS-encoded cellulose strip, which achieved 3.98 × 10 8 SERS-EF, 6.1%-RSD reproducibility, and <10%-degraded sustainability, implicated the possibility of practical applications in high analytical screening methods, such as single-molecule detection. The remarkable sensitivity and selectivity of this bimetallic biosensing strip in determining aquatic toxicities for prohibited drugs, such as aniline, sodium azide, and malachite green, as well as monitoring the breast cancer progression for urine, confirmed its potential as a low-cost label-free point-of-care test chip for the early diagnosis of human diseases.
Melancon, Marites; Lu, Wei; Li, Chun
2009-06-01
Nanoparticles with gold shell and iron core have unique optical and magnetic properties which can be utilized for simultaneous detection and treatment strategies. Several nanoparticles have been synthesized and shown to mediate a variety of potential applications in biomedicine, including cancer molecular optical and magnetic resonance imaging, controlled drug delivery, and photothermal ablation therapy. However, to be effective, these nanoparticles must be delivered efficiently into their targets. In this review, we will provide an updated summary of the gold-shelled magnetic nanoparticles that have been synthesized, methods for characterization, and their potential for cancer diagnosis and treatment. We will also discuss the biological barriers that need to be overcome for the effective delivery of these nanoparticles. The desired nanoparticle characteristics needed to evade these biological barriers were also explained. Hopefully, this review will help researchers in designing nanoparticles by carefully choosing the optimum size, shape, surface charge, and surface coating.
Synthesis of Core-Shell Nanoparticle Composites
2010-08-17
Mawson Institute, University of South Australia 1 Final Report Contract Number FA2386-09-1-4043 Synthesis of Core-Shell Nanoparticle Composites...CI: Peter Majewski, School of Advanced Manufacturing and Mechanical Engineering, Mawson Institute, University of South Australia, peter.majewski...5f. WORK UNIT NUMBER 7. PERFORMING ORGANIZATION NAME(S) AND ADDRESS(ES) University of South Australia, Mawson Lakes Blvd., Mawson Lakes SA, Australia
Adsorption of cadmium on cerium oxide nanoparticles and oyster shells
NASA Astrophysics Data System (ADS)
Ji, Yongbo; Liu, Zhuomiao; Dang, Yonghui; Xu, Lina; Ning, Fangyuan; Xue, Yinhao; Wei, Yongpeng; Dai, Yanhui
2018-03-01
This study investigated the adsorption of cadmium (Cd(II)) by cerium oxide nanoparticles (CeO2 NPs) and oyster shells in seawater. The results showed that the addition of Cd(II) significantly inhibited the agglomeration of CeO2 NPs both in DI water and seawater, increased the positive charges of CeO2 NPs in DI water and neutralized the negative charges of CeO2 NPs in seawater. Additionally, CeO2 NPs could adsorb Cd and the bioavailability of Cd was reduced in the presence of oyster shells. This study demonstrated that the adsorption of metals on shells should not be neglected for the accumulation of metals by shellfish.
PLGA/polymeric liposome for targeted drug and gene co-delivery.
Wang, Hanjie; Zhao, Peiqi; Su, Wenya; Wang, Sheng; Liao, Zhenyu; Niu, Ruifang; Chang, Jin
2010-11-01
Chemotherapy is one of the most effective approaches to treat cancers in the clinic, but the problems, such as multidrug resistance (MDR), low bioavailability and toxicity, severely constrain the further application of chemotherapy. Our group recently reported that cationic PLGA/folate coated PEGlated polymeric liposome core-shell nanoparticles (PLGA/FPL NPs). It was self-assembled from a hydrophobic PLGA core and a hydrophilic folate coated PEGlated lipid shell for targeting co-delivery of drug and gene. Hydrophobic drugs can be incorporated into the core and the cationic shell of the drug-loaded nanoparticles can be used to bind DNA. The drug-loaded PLGA/FPL NPs/DNA complexes offer advantages to overcome these problems mentioned above, such as co-delivery of drugs and DNA to improving the chemosensitivity of cancer cells at a gene level, and targeting delivery of drug to the cancer tissue that enhance the bioavailability and reduce the toxicity. The experiment showed that nanoparticles have core-shell structure with nanosize, sustained drug release profile and good DNA-binding ability. Importantly, the core-shell nanoparticles achieve the possibility of co-delivering drugs and genes to the same cells with high gene transfection and drug delivery efficiency. Our data suggest that the PLGA/FPL NPs may be a useful drug and gene co-delivery system. Copyright © 2010 Elsevier Ltd. All rights reserved.
NASA Astrophysics Data System (ADS)
Yao, Tongjie; Cui, Tieyu; Wang, Hao; Xu, Linxu; Cui, Fang; Wu, Jie
2014-06-01
Metal nanoparticles are promising catalysts for dye degradation in treating wastewater despite the challenges of recycling and stability. In this study, we have introduced a simple way to prepare Au@polypyrrole (PPy)/Fe3O4 catalysts with Au nanoparticles embedded in a PPy/Fe3O4 capsule shell. The PPy/Fe3O4 capsule shell used as a support was constructed in one-step, which not only dramatically simplified the preparation process, but also easily controlled the magnetic properties of the catalysts through adjusting the dosage of FeCl2.4H2O. The component Au nanoparticles could catalyze the reduction of methylene blue dye with NaBH4 as a reducing agent and the reaction rate constant was calculated through the pseudo-first-order reaction equation. The Fe3O4 nanoparticles permitted quick recycling of the catalysts with a magnet due to their room-temperature superparamagnetic properties; therefore, the catalysts exhibited good reusability. In addition to catalytic activity and reusability, stability is also an important property for catalysts. Because both Au and Fe3O4 nanoparticles were wrapped in the PPy shell, compared with precursor polystyrene/Au composites and bare Fe3O4 nanoparticles, the stability of Au@PPy/Fe3O4 hollow capsules was greatly enhanced. Since the current method is simple and flexible to create recyclable catalysts with high stability, it would promote the practicability of metal nanoparticle catalysts in industrial polluted water treatment.Metal nanoparticles are promising catalysts for dye degradation in treating wastewater despite the challenges of recycling and stability. In this study, we have introduced a simple way to prepare Au@polypyrrole (PPy)/Fe3O4 catalysts with Au nanoparticles embedded in a PPy/Fe3O4 capsule shell. The PPy/Fe3O4 capsule shell used as a support was constructed in one-step, which not only dramatically simplified the preparation process, but also easily controlled the magnetic properties of the catalysts through adjusting the dosage of FeCl2.4H2O. The component Au nanoparticles could catalyze the reduction of methylene blue dye with NaBH4 as a reducing agent and the reaction rate constant was calculated through the pseudo-first-order reaction equation. The Fe3O4 nanoparticles permitted quick recycling of the catalysts with a magnet due to their room-temperature superparamagnetic properties; therefore, the catalysts exhibited good reusability. In addition to catalytic activity and reusability, stability is also an important property for catalysts. Because both Au and Fe3O4 nanoparticles were wrapped in the PPy shell, compared with precursor polystyrene/Au composites and bare Fe3O4 nanoparticles, the stability of Au@PPy/Fe3O4 hollow capsules was greatly enhanced. Since the current method is simple and flexible to create recyclable catalysts with high stability, it would promote the practicability of metal nanoparticle catalysts in industrial polluted water treatment. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00023d
Ansari, Anees A
2018-02-01
Samarium (Sm3+)-doped LaF3 nanoparticles (NPs) subsequently encapsulated with inert crystalline LaF3 and amorphous silica layers were prepared by polyol and sol-gel chemical process, respectively. These surface modified core/shell/SiO2-nanostructured were characterized by X-ray diffraction (XRD), FE-transmission electron microscopy (TEM), thermal analysis, FTIR, UV/Vis absorption, bang gap energy and photoluminescence spectroscopy. The FETEM, EDX and FTIR spectral studies clearly revealed that the silica layer has been formed surrounding the core-NPs. Comparative spectral analysis indicated that core/shell/SiO2-NPs revealed high solubility in aqueous and non-aqueous solvents. The decrease in band gap energy after surface growth of an inert LaF3 and silica shells is directly correlated to the increase in grain size. On comparing the emission intensity, a significant enhancement was observed after inert layer coating, whereas, it suppress after silica encapsulation due to the non-radiative transitions. The increase luminescent intensity after inert shell growth indicates that a significant amount of non-radiative centers existing on the surface of core/shell nanoparticles can be eliminated by the shielding effect of LaF3 shells. These observed results indicate that the as-prepared core/shell/SiO2-NPs could be highly useful in broad photonic based applications such as optical sensor/optical bio-probe and light emitting diode.
NASA Astrophysics Data System (ADS)
Kübler, Markus; Jurzinsky, Tilman; Ziegenbalg, Dirk; Cremers, Carsten
2018-01-01
In this work the relationship between structural composition and electrochemical characteristics of Palladium(Pd)-Ruthenium(Ru) nanoparticles during alkaline methanol oxidation reaction is investigated. The comparative study of a standard alloyed and a precisely Ru-core-Pd-shell structured catalyst allows for a distinct investigation of the electronic effect and the bifunctional mechanism. Core-shell catalysts benefit from a strong electronic effect and an efficient Pd utilization. It is found that core-shell nanoparticles are highly active towards methanol oxidation reaction for potentials ≥0.6 V, whereas alloyed catalysts show higher current outputs in the lower potential range. However, differential electrochemical mass spectrometry (DEMS) experiments reveal that the methanol oxidation reaction on core-shell structured catalysts proceeds via the incomplete oxidation pathway yielding formaldehyde, formic acid or methyl formate. Contrary, the alloyed catalyst benefits from the Ru atoms at its surface. Those are found to be responsible for high methanol oxidation activity at lower potentials as well as for complete oxidation of CH3OH to CO2 via the bifunctional mechanism. Based on these findings a new Ru-core-Pd-shell-Ru-terrace catalyst was synthesized, which combines the advantages of the core-shell structure and the alloy. This novel catalyst shows high methanol electrooxidation activity as well as excellent selectivity for the complete oxidation pathway.
Chen, Chih-Jung; Chiang, Ray-Kuang; Kamali, Saeed; Wang, Sue-Lein
2015-09-14
Cobalt-doped wüstite (CWT), Co0.33Fe0.67O, nanoparticles were prepared via the thermal decomposition of CoFe2-oleate complexes in organic solvents. A controllable oxidation process was then performed to obtain Co0.33Fe0.67O/CoFe2O4 core-shell structures with different core-to-shell volume ratios and exchange bias properties. The oxidized core-shell samples with a ∼4 nm CoFe2O4 shell showed good resistance to oxygen transmission. Thus, it is inferred that the cobalt ferrite shell provides a better oxidation barrier performance than magnetite in the un-doped case. The hysteresis loops of the oxidized 19 nm samples exhibited a high exchange bias field (H(E)), an enhanced coercivity field (H(C)), and a pronounced vertical shift, thus indicating the presence of a strong exchange bias coupling effect. More importantly, the onset temperature of H(E) was found to be higher than 200 K, which suggests that cobalt doping increases the Néel temperature (T(N)) of the CWT core. In general, the results show that the homogeneous dispersion of Co in iron precursors improves the stability of the final CWT nanoparticles. Moreover, the CoFe2O4 shells formed following oxidation increase the oxidation resistance of the CWT cores and enhance their anisotropy energy.
Wang, Yitong; Wang, Ling; Yan, Miaomiao; Dong, Shuli; Hao, Jingcheng
2017-08-30
Functional DNA molecules have been introduced into polymer-based nanocarrier systems to incorporate chemotherapy drugs for cancer therapy. Here is the first report of dual-responsive microgels composed of a core of Au nanorods and a shell of magnetic ionic liquid and DNA moieties in the cross-linking network simultaneously, as effective drug delivery vectors. TEM images indicated a magnetic polymer shell has an analogous "doughnut" shape which loosely surround the AuNRs core. When irradiated with a near-infrared-light (near-IR) laser, Au nanorods are the motors which convert the light to heat, leading to the release of the encapsulated payloads with high controllability. DNA acts not only as a cross-linker agent, but also as a gatekeeper to regulate the release of drugs. The internalization study and MTT assay confirm that these core-shell DNA microgels are excellent candidates which can enhance the cytotoxicity of cancer cells controlled by near-IR laser and shield the high toxicity of chemotherapeutic agents to improve the killing efficacy of chemotherapeutic agents efficiently in due course.
Functional Polymer Opals and Porous Materials by Shear-Induced Assembly of Tailor-Made Particles.
Gallei, Markus
2018-02-01
Photonic band-gap materials attract enormous attention as potential candidates for a steadily increasing variety of applications. Based on the preparation of easily scalable monodisperse colloids, such optically attractive photonic materials can be prepared by an inexpensive and convenient bottom-up process. Artificial polymer opals can be prepared by shear-induced assembly of core/shell particles, yielding reversibly stretch-tunable materials with intriguing structural colors. This feature article highlights recent developments of core/shell particle design and shear-induced opal formation with focus on the combination of hard and soft materials as well as crosslinking strategies. Structure formation of opal materials relies on both the tailored core/shell architecture and the parameters for polymer processing. The emphasis of this feature article is on elucidating the particle design and incorporation of addressable moieties, i.e., stimuli-responsive polymers as well as elaborated crosslinking strategies for the preparation of smart (inverse) opal films, inorganic/organic opals, and ceramic precursors by shear-induced ordering. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
Surface-engineered core-shell nano-size ferrites and their antimicrobial activity
DOE Office of Scientific and Technical Information (OSTI.GOV)
Baraliya, Jagdish D., E-mail: jdbaraliya@yahoo.co.in; Joshi, Hiren H., E-mail: jdbaraliya@yahoo.co.in
We report the results of biological study on core-shell structured MFe{sub 2}O{sub 4} (where M = Co, Mn, Ni) nanoparticles and influence of silica- DEG dual coating on their antimicrobial activity. Spherical MFe{sub 2}O{sub 4} nanoparticles were prepared via a Co-precipitation method. The microstructures and morphologies of these nanoparticles were studied by x-ray diffraction and FTIR. The antimicrobial activity study carried out in nutrient agar medium with addition of antimicrobial synthesis compound which is tested for its activity against different types of bacteria.
NASA Astrophysics Data System (ADS)
Stević, Dragana; Mihajlović, Dijana; Kukobat, Radovan; Hattori, Yoshiyuki; Sagisaka, Kento; Kaneko, Katsumi; Atlagić, Suzana Gotovac
2016-08-01
Hematite nanoparticles with amorphous, yet relatively uniform carbon shell, were produced based exclusively on the waste sludge from the iron mine as the raw material. The procedure for acid digestion-based purification of the sludge with the full recovery of acid vapors and the remaining non-toxic rubble is described. Synthesis of the hematite nanoparticles was performed by the arrested precipitation method with cationic surfactant. The particles were thoroughly characterized and the potential of their economical production for the battery industry is indicated.
2004-09-30
nanoparticles that consist of a polymer coated ?-Fe2O3 superparamagnetic core and CdSe/ZnS quantum dots (QDs) shell. A single layer of QDs was bound to the...Fe2O3) with polymer coating, the scale bar is 20 nm; b) A TEM image of QDs magnetic beads core-shell nanoparticles. The scale bar is 20 nm. c) A High...common practice in microfluidic/GMR sensor integration is using hybrid approaches by adding-on polymer based fluidic structures (such as PDMS fluidic
Surface-engineered core-shell nano-size ferrites and their antimicrobial activity
NASA Astrophysics Data System (ADS)
Baraliya, Jagdish D.; Joshi, Hiren H.
2014-04-01
We report the results of biological study on core-shell structured MFe2O4 (where M = Co, Mn, Ni) nanoparticles and influence of silica- DEG dual coating on their antimicrobial activity. Spherical MFe2O4 nanoparticles were prepared via a Co-precipitation method. The microstructures and morphologies of these nanoparticles were studied by x-ray diffraction and FTIR. The antimicrobial activity study carried out in nutrient agar medium with addition of antimicrobial synthesis compound which is tested for its activity against different types of bacteria.
Vecchione, Donatella; Aiello, Marco; Cavaliere, Carlo; Nicolai, Emanuele; Netti, Paolo Antonio; Torino, Enza
2017-09-01
Although there has been an improvement in the hardware and software of the PET/MRI system, the development of the nanoprobes exploiting the simultaneous acquisition of the bimodal data is still under investigation. Moreover, few studies on biocompatible and clinically relevant probes are available. This work presents a core-shell polymeric nanocarrier with improved relaxometric properties for simultaneous PET/MRI acquisitions. Core-shell nanoparticles entrapping the Gd-DTPA and 18 F-FDG are obtained by a complex coacervation. The boosting of r 1 of the entrapped Gd-DTPA up to five-times compared with 'free Gd-DTPA', is confirmed by the PET/MRI scan. The sorption of 18 F-FDG into the nanoparticles is studied and designed to be integrated downstream for the production of the tracer.
Diffraction data of core-shell nanoparticles from an X-ray free electron laser
Li, Xuanxuan; Chiu, Chun -Ya; Wang, Hsiang -Ju; ...
2017-04-11
X-ray free-electron lasers provide novel opportunities to conduct single particle analysis on nanoscale particles. Coherent diffractive imaging experiments were performed at the Linac Coherent Light Source (LCLS), SLAC National Laboratory, exposing single inorganic core-shell nanoparticles to femtosecond hard-X-ray pulses. Each facetted nanoparticle consisted of a crystalline gold core and a differently shaped palladium shell. Scattered intensities were observed up to about 7 nm resolution. Analysis of the scattering patterns revealed the size distribution of the samples, which is consistent with that obtained from direct real-space imaging by electron microscopy. Furthermore, scattering patterns resulting from single particles were selected and compiledmore » into a dataset which can be valuable for algorithm developments in single particle scattering research.« less
Fabrication of superhydrophobic fluorinated silica nanoparticles for multifunctional liquid marbles
NASA Astrophysics Data System (ADS)
Shang, Qianqian; Hu, Lihong; Hu, Yun; Liu, Chengguo; Zhou, Yonghong
2018-01-01
A facile one-pot method for the fabrication of superhydrophobic fluorinated silica nanoparticles is reported. Fluorinated aggregated silica (A-SiO2/FAS) nanoparticles were synthesized by controlling the nanoparticles assembly, in situ fixation and overgrowth of particle seeds with the assist of tetraethoxysilane (TEOS) in ethanol/water solution and then modification with fluoroalkylsilane (FAS) molecules. Such kind of A-SiO2/FAS nanoparticles showed superhydrophobicity and was not wetted by water, thus it could be served as the encapsulating shells to manipulate liquid droplets. Liquid marbles fabricated from A-SiO2/FAS nanoparticles were used for ammonia gas sensing or emitting by taking advantage of the porosity and superhydrophobicity of the liquid marble shells. In addition, the posibility of A-SiO2/FAS-based liquid marbles as microreactor for dopamine polymerization also was explored.
Multi-walled carbon/IF-WS2 nanoparticles with improved thermal properties
NASA Astrophysics Data System (ADS)
Xu, Fang; Almeida, Trevor P.; Chang, Hong; Xia, Yongde; Wears, M. Lesley; Zhu, Yanqiu
2013-10-01
A unique new class of core-shell structured composite nanoparticles, C-coated inorganic fullerene-like WS2 (IF-WS2) hollow nanoparticles, has been created for the first time in large quantities, by a continuous chemical vapour deposition method using a rotary furnace. Transmission electron microscopy and Raman characterisations of the resulting samples reveal that the composite nanoparticles exhibited a uniform shell of carbon coating, ranging from 2-5 nm on the IF-WS2 core, with little or no agglomeration. Importantly, thermogravimetric analysis and differential scanning calorimetry analysis confirm that their thermal stability against oxidation in air has been improved by about 70 °C, compared to the pristine IF-WS2, making these new C-coated IF-WS2 nanoparticles more attractive for critical engineering applications.A unique new class of core-shell structured composite nanoparticles, C-coated inorganic fullerene-like WS2 (IF-WS2) hollow nanoparticles, has been created for the first time in large quantities, by a continuous chemical vapour deposition method using a rotary furnace. Transmission electron microscopy and Raman characterisations of the resulting samples reveal that the composite nanoparticles exhibited a uniform shell of carbon coating, ranging from 2-5 nm on the IF-WS2 core, with little or no agglomeration. Importantly, thermogravimetric analysis and differential scanning calorimetry analysis confirm that their thermal stability against oxidation in air has been improved by about 70 °C, compared to the pristine IF-WS2, making these new C-coated IF-WS2 nanoparticles more attractive for critical engineering applications. Electronic supplementary information (ESI) available: Sketch of the rotary furnace, XRD pattern comparison of IF-WS2 and 2H WS2, XRD patterns of C-coated IF-WS2 (41-50°), and TGA and MS curves for pristine IF-WS2. See DOI: 10.1039/c3nr03844k
Yolk@Shell Nanoarchitectures with Bimetallic Nanocores-Synthesis and Electrocatalytic Applications.
Guiet, Amandine; Unmüssig, Tobias; Göbel, Caren; Vainio, Ulla; Wollgarten, Markus; Driess, Matthias; Schlaad, Helmut; Polte, Jörg; Fischer, Anna
2016-10-10
In the present paper, we demonstrate a versatile approach for the one-pot synthesis of metal oxide yolk@shell nanostructures filled with bimetallic nanocores. This novel approach is based on the principles of hydrophobic nanoreactor soft-templating and is exemplified for the synthesis of various AgAu NP @tin-rich ITO (AgAu@ITO TR ) yolk@shell nanomaterials. Hydrophobic nanoreactor soft-templating thereby takes advantage of polystyrene-block-poly(4-vinylpiridine) inverse micelles as two-compartment nanoreactor template, in which the core and the shell of the micelles serve as metal and metal oxide precursor reservoir, respectively. The composition, size and number of AuAg bimetallic nanoparticles incorporated within the ITO TR yolk@shell can easily be tuned. The conductivity of the ITO TR shell and the bimetallic composition of the AuAg nanoparticles, the as-synthesized AuAg NP @ITO TR yolk@shell materials could be used as efficient electrocatalysts for electrochemical glucose oxidation with improved onset potential when compared to their gold counterpart.
Xu, You; Li, Yinghao; Yin, Shuli; Yu, Hongjie; Xue, Hairong; Li, Xiaonian; Wang, Hongjing; Wang, Liang
2018-06-01
Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy-carbon core-shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10-30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2-6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.
Yang, Meicheng; Gao, Lipeng; Liu, Kai; Luo, Chunhua; Wang, Yiting; Yu, Lei; Peng, Hui; Zhang, Wen
2015-01-01
Core/shell/shell structured Fe3O4/SiO2/Gd2O(CO3)2 nanoparticles were successfully synthesized. Their properties as a new type of T1-T2 dual model contrast agent for magnetic resonance imaging were investigated. Due to the introduce of a separating SiO2 layer, the magnetic coupling between Gd2O(CO3)2 and Fe3O4 could be modulated by the thickness of SiO2 layer and produce appropriate T1 and T2 signal. Additionally, the existence of Gd(3+) enhances the transverse relaxivity of Fe3O4 possibly because of the magnetic coupling between Gd(3+) and Fe3O4. The Fe3O4/SiO2/Gd2O(CO3)2 nanoparticles exhibit good biocompatibility, showing great potential for biomedical applications. Copyright © 2014 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Benhadjala, W., E-mail: warda.benhadjala@cea.fr; CEA, LETI, Minatec Campus, 38000 Grenoble; Gravoueille, M.
2015-11-23
Extensive research is being conducted on the development of inorganic/organic nanocomposites for a wide variety of applications in microelectronics, biotechnologies, photonics, adhesives, or optical coatings. High filler contents are usually required to fully optimize the nanocomposites properties. However, numerous studies demonstrated that traditional composite viscosity increases with increasing the filler concentration reducing therefore significantly the material processability. In this work, we synthesized inorganic/organic core-shell nanocomposites with different shell thicknesses. By reducing the shell thickness while maintaining a constant core size, the nanoparticle molecular mass decreases but the nanocomposite filler fraction is correlatively increased. We performed viscosity measurements, which clearly highlightedmore » that intrinsic viscosity of hybrid nanoparticles decreases as the molecular mass decreases, and thus, as the filler fraction increases, as opposed to Einstein predictions about the viscosity of traditional inorganic/polymer two-phase mixtures. This exceptional behavior, modeled by Mark-Houwink-Sakurada equation, proves to be a significant breakthrough for the development of industrializable nanocomposites with high filler contents.« less
NASA Astrophysics Data System (ADS)
Xu, You; Li, Yinghao; Yin, Shuli; Yu, Hongjie; Xue, Hairong; Li, Xiaonian; Wang, Hongjing; Wang, Liang
2018-06-01
Design of highly active and cost-effective electrocatalysts is very important for the generation of hydrogen by electrochemical water-splitting. Herein, we report the fabrication of ultrathin nitrogen-doped graphitized carbon shell encapsulating CoRu bimetallic nanoparticles (CoRu@NCs) and demonstrate their promising feasibility for efficiently catalyzing the hydrogen evolution reaction (HER) over a wide pH range. The resultant CoRu@NC nanohybrids possess an alloy–carbon core–shell structure with encapsulated low-ruthenium-content CoRu bimetallic alloy nanoparticles (10–30 nm) as the core and ultrathin nitrogen-doped graphitized carbon layers (2–6 layers) as the shell. Remarkably, the optimized catalyst (CoRu@NC-2 sample) with a Ru content as low as 2.04 wt% shows superior catalytic activity and excellent durability for HER in acidic, neutral, and alkaline conditions. This work offers a new method for the design and synthesis of non-platium-based electrocatalysts for HER in all-pH.
NASA Astrophysics Data System (ADS)
Metzman, Jonathan S.; Ridley, Jason I.; Khalifa, Moataz B.; Heflin, James R.
2015-12-01
A modified silica nanoparticle (MSNP) solution was formed by the encapsulation of negatively charged silica nanoparticles by the UV-crosslinkable polycation oligomer diazo-resin (DAR). Appropriate DAR encapsulation concentrations were determined by use of zeta-potential and dynamic light scattering measurements. The MSNPs were used in conjunction with poly(styrene sulfonate) (PSS) to grow homogenous ionic self-assembled multilayer anti-reflection coatings. Stability was induced within the films by the exposure of UV-irradiation that allowed for crosslinking of the DAR and PSS. The films were characterized by UV/vis/IR spectroscopy and field emission scanning electron microscopy. The transmission and reflection levels were >98.5% and <0.05%, respectively. The refractive indices resided in the 1.25-1.26 range. The solvent stability was tested by sonication of the films in a ternary solvent (H2O/DMF/ZnCl2 3:5:2 w/w/w).
NASA Astrophysics Data System (ADS)
Zhang, A. Ping; He, Sailing; Kim, Kyoung Tae; Yoon, Yong-Kyu; Burzynski, Ryszard; Samoc, Marek; Prasad, Paras N.
2008-11-01
We report on the fabrication of nanoparticle/polymer submicron structures by combining holographic lithography and reactive ion etching. Silica nanoparticles are uniformly dispersed in a (SU8) polymer matrix at a high concentration, and in situ polymerization (cross-linking) is used to form a nanoparticle/polymer composite. Another photosensitive SU8 layer cast upon the nanoparticle/SU8 composite layer is structured through holographic lithography, whose pattern is finally transferred to the nanoparticle/SU8 layer by the reactive ion etching process. Honeycomb structures in a submicron scale are experimentally realized in the nanoparticle/SU8 composite.
NASA Astrophysics Data System (ADS)
Tóth, Ildikó Y.; Illés, Erzsébet; Szekeres, Márta; Tombácz, Etelka
2015-04-01
Polysaccharides are promising candidates for manufacturing biocompatible core-shell nanoparticles with potential in vivo use. Superparamagnetic magnetite nanoparticles (MNPs) have prospective application in both diagnosis and therapy, and so developing a novel polysaccharide shell on MNP core is of great challenge. MNPs were prepared by co-precipitation, then the surface of purified MNPs was coated with chondroitin-sulfate-A (CSA) to obtain core-shell structured magnetite nanoparticles (CSA@MNP). The effect of the added amount of CSA on the surface charging and the aggregation state of MNPs at various pHs and 10 mM NaCl was measured by electrophoresis and dynamic light scattering. The amphoteric behavior of MNPs was fundamentally modified by adsorption of CSA polyanions. A very low CSA-loading induces the aggregation of MNPs, while four times more stabilizes the dispersions over the whole pH-range studied. The coagulation kinetics experiments measured at pH=6.3±0.3 showed that salt tolerance of CSA@MNPs rises up to ~150 mM NaCl.
Supramolecular core-shell nanoparticles for photoconductive device applications
NASA Astrophysics Data System (ADS)
Cheng, Chih-Chia; Chen, Jem-Kun; Shieh, Yeong-Tarng; Lee, Duu-Jong
2016-08-01
We report a breakthrough discovery involving supramolecular-based strategies to construct novel core-shell heterojunction nanoparticles with hydrophilic adenine-functionalized polythiophene (PAT) as the core and hydrophobic phenyl-C61-butyric acid methyl ester (PCBM) as the shell, which enables the conception of new functional supramolecular assemblies for constructing functional nanomaterials for applications in optoelectronic devices. The generated nanoparticles exhibit uniform spherical shape, well-controlled tuning of particle size with narrow size distributions, and excellent electrochemical stability in solution and the solid state owing to highly efficient energy transfer from PAT to PCBM. When the PAT/PCBM nanoparticles were fabricated into a photoconducting layer in an electronic device, the resulting device showed excellent electric conduction characteristics, including an electrically-tunable voltage-controlled switch, and high short-circuit current and open-circuit voltage. These observations demonstrate how the self-assembly of PAT/PCBM into specific nanostructures may help to promote efficient charge generation and transport processes, suggesting potential for a wide variety of applications as a promising candidate material for bulk heterojunction polymer devices.
NASA Astrophysics Data System (ADS)
Dasri, Thananchai; Chingsungnoen, Artit
2018-06-01
Surface plasmon in nano-sized particles, such as gold, silver, copper and their composites, has recently attracted a great deal of attention due to its possible uses in many applications, especially in life sciences. It is desirable for application devices with a tenability of surface plasmon wavelength and optical properties enhancement. This article presents enhanced optical light absorption and tunable wavelength in gold-coated magnetite (Fe3O4@Au core-shell) nanoparticles embedded in water using the theoretical method of discrete dipole approximation (DDA). The absorption spectra in the wavelengths from 350 to 900 nm were found to be the spectra obtained from Fe3O4@Au core-shell nanoparticles, and when compared with pure Fe3O4 nanoparticles, the surface plasmon resonance can be enhanced and tuned over the entire visible spectrum (viz. 350-800 nm) of the electromagnetic spectrum by varying the Au shell thickness (2-5 nm). Similarly, the Faraday rotation spectra can also be obtained.
NASA Astrophysics Data System (ADS)
Tregubov, A. A.; Sokolov, I. L.; Babenyshev, A. V.; Nikitin, P. I.; Cherkasov, V. R.; Nikitin, M. P.
2018-03-01
Multifunctional hybrid nanocomposites remain to be of great interest in biomedicine as a universal tool in a number of applications. As a promising example, the nanoparticles with magnetic core and porous shell have a potential as theranostic agents combining both the diagnostics probe and drug delivery vehicle properties. However, reported methods of the nanostructure preparation are complex and include tedious time-consuming growth of porous shell by means of layer by layer assembly technique. In this study, we develop new way of fabrication of the superparamagnetic magnetite core @ porous metal organic framework shell nanoparticles and demonstrate their application both as a multimodal (MRI contrasting, magnetometric and optical labeling) and multifunctional (in vivo bioimaging, biotargeting by coupled receptors, lateral flow assay) agents. The easiness of fabrication, controllable bioconjugation properties and low level of non-specific binding indicate high potential of the nanoparticles to be employed as multifunctional agents in theranostics, advanced biosensing and bioimaging.
Development of magneto-plasmonic nanoparticles for multimodal image-guided therapy to the brain.
Tomitaka, Asahi; Arami, Hamed; Raymond, Andrea; Yndart, Adriana; Kaushik, Ajeet; Jayant, Rahul Dev; Takemura, Yasushi; Cai, Yong; Toborek, Michal; Nair, Madhavan
2017-01-05
Magneto-plasmonic nanoparticles are one of the emerging multi-functional materials in the field of nanomedicine. Their potential for targeting and multi-modal imaging is highly attractive. In this study, magnetic core/gold shell (MNP@Au) magneto-plasmonic nanoparticles were synthesized by citrate reduction of Au ions on magnetic nanoparticle seeds. Hydrodynamic size and optical properties of magneto-plasmonic nanoparticles synthesized with the variation of Au ions and reducing agent concentrations were evaluated. The synthesized magneto-plasmonic nanoparticles exhibited superparamagnetic properties, and their magnetic properties contributed to the concentration-dependent contrast in magnetic resonance imaging (MRI). The imaging contrast from the gold shell part of the magneto-plasmonic nanoparticles was also confirmed by X-ray computed tomography (CT). The transmigration study of the magneto-plasmonic nanoparticles using an in vitro blood-brain barrier (BBB) model proved enhanced transmigration efficiency without disrupting the integrity of the BBB, and showed potential to be used for brain diseases and neurological disorders.
The pH sensitive properties of carboxymethyl chitosan nanoparticles cross-linked with calcium ions.
Kalliola, Simo; Repo, Eveliina; Srivastava, Varsha; Heiskanen, Juha P; Sirviö, Juho Antti; Liimatainen, Henrikki; Sillanpää, Mika
2017-05-01
In environmental applications the applied materials are required to be non-toxic and biodegradable. Carboxymethyl chitosan nanoparticles cross-linked with Ca 2+ ions (CMC-Ca) fulfill these requirements, and they are also renewable. These nanoparticles were applied to oil-spill treatment in our previous study and here we focused on enhancing their properties. It was found that while the divalent Ca 2+ ions are crucial for the formation of the CMC-Ca, the attractive interaction between NH 3 + and COO - groups contributed significantly to the formation and stability of the CMC-Ca. The stability decreased as a function of pH due to the deprotonation of the amino groups. Therefore, the nanoparticles were found to be fundamentally pH sensitive in solution, if the pH deviated from the pH (7-9) that was used in the synthesis of the nanoparticles. The pH sensitive CMC-Ca synthesized in pH 7 and 8 were most stable in the studied conditions and could find applications in oil-spill treatment or controlled-release of substances. Copyright © 2017 The Authors. Published by Elsevier B.V. All rights reserved.
Molecularly Imprinted Biodegradable Nanoparticles
NASA Astrophysics Data System (ADS)
Gagliardi, Mariacristina; Bertero, Alice; Bifone, Angelo
2017-01-01
Biodegradable polymer nanoparticles are promising carriers for targeted drug delivery in nanomedicine applications. Molecu- lar imprinting is a potential strategy to target polymer nanoparticles through binding of endogenous ligands that may promote recognition and active transport into specific cells and tissues. However, the lock-and-key mechanism of molecular imprinting requires relatively rigid cross-linked structures, unlike those of many biodegradable polymers. To date, no fully biodegradable molecularly imprinted particles have been reported in the literature. This paper reports the synthesis of a novel molecularly- imprinted nanocarrier, based on poly(lactide-co-glycolide) (PLGA) and acrylic acid, that combines biodegradability and molec- ular recognition properties. A novel three-arm biodegradable cross-linker was synthesized by ring-opening polymerization of glycolide and lactide initiated by glycerol. The resulting macromer was functionalized by introduction of end-functions through reaction with acryloyl chloride. Macromer and acrylic acid were used for the synthesis of narrowly-dispersed nanoparticles by radical polymerization in diluted conditions in the presence of biotin as template molecule. The binding capacity of the imprinted nanoparticles towards biotin and biotinylated bovine serum albumin was twentyfold that of non-imprinted nanoparti- cles. Degradation rates and functional performances were assessed in in vitro tests and cell cultures, demonstrating effective biotin-mediated cell internalization.
Design of Aerosol Coating Reactors: Precursor Injection
Buesser, Beat; Pratsinis, Sotiris E.
2013-01-01
Particles are coated with thin shells to facilitate their processing and incorporation into liquid or solid matrixes without altering core particle properties (coloristic, magnetic, etc.). Here, computational fluid and particle dynamics are combined to investigate the geometry of an aerosol reactor for continuous coating of freshly-made titanium dioxide core nanoparticles with nanothin silica shells by injection of hexamethyldisiloxane (HMDSO) vapor downstream of TiO2 particle formation. The focus is on the influence of HMDSO vapor jet number and direction in terms of azimuth and inclination jet angles on process temperature and coated particle characteristics (shell thickness and fraction of uncoated particles). Rapid and homogeneous mixing of core particle aerosol and coating precursor vapor facilitates synthesis of core-shell nanoparticles with uniform shell thickness and high coating efficiency (minimal uncoated core and free coating particles). PMID:23658471
Kohsari, Iraj; Shariatinia, Zahra; Pourmortazavi, Seied Mahdi
2016-10-01
Antimicrobial chitosan-polyethylene oxide (CS-PEO) nanofiber mats loaded with 3, 5 and 10% (w/w) of zeolitic imidazolate framework-8 nanoparticles (ZIF-8 NPs, ∼60nm diameter) were developed by electrospinning technique. The CS-PEO-GA-3% ZIF-8 NPs crosslinked with glutaraldehyde (GA) vapor was also prepared. The electrospun mats were characterized by various analysis including FE-SEM, EDAX, elemental mapping, FT-IR, contact angle, TGA/DSC as well as tensile strength analysis. The nanofibers had average diameters within the range ∼70-120nm. Antimicrobial activities of the CS-PEO and CS-PEO-3% ZIF-8 mats were evaluated by the viable cell-counting method for determining their effectiveness in reducing or halting the growth of Staphylococcus aureus and Escherichia coli bacteria so that the CS-PEO mat containing 3% ZIF-8 revealed 100% bactericidal activity against both kinds of bacteria. The crosslinked CS-PEO-GA-3% ZIF-8 NPs sample was less thermally stable but more hydrophilic than its related non-crosslinked mat reflecting there was no need to crosslink the fibers using a chemical crosslinker having adverse effects. The highest hydrophobicity and appropriate thermal and tensile properties of CS-PEO-3% ZIF-8 NPs among those of the mats including 5 and 10% ZIF-8 NPs suggested that the mentioned mat is the most suitable sample for food coating applications. Copyright © 2016 Elsevier B.V. All rights reserved.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Wang, Chenyu; Sang, Xiahan; Gamler, Jocelyn T. L.
Compressive surface strains can enhance the performance of platinum-based core@shell electrocatalysts for the oxygen reduction reaction (ORR). Bimetallic core@shell nanoparticles (NPs) are widely studied nanocatalysts but often have limited lattice mismatch and surface compositions; investigations of core@shell NPs with greater compositional complexity and lattice misfit are in their infancy. Here, a new class of multimetallic NPs composed of intermetallic cores and random alloy shells is reported. Specifically, face-centered cubic (fcc) Pt- Cu random alloy shells were deposited non-epitaxially on PdCu B2 intermetallic seeds, giving rise to faceted core@shell NPs with highly strained surfaces. In fact, high resolution transmission electron microscopymore » (HRTEM) revealed orientation-dependent surface strains, where the compressive strains were minimal on Pt-Cu {111} facets but greater on {200} facets. These core@shell NPs provide higher specific and mass activities for the ORR when compared to conventional Pt-Cu NPs. Moreover, these intermetallic@random alloy NPs displayed high endurance, undergoing 10,000 cycles with only a slight decay in activity and no apparent structural changes.« less
Wang, Chenyu; Sang, Xiahan; Gamler, Jocelyn T. L.; ...
2017-08-25
Compressive surface strains can enhance the performance of platinum-based core@shell electrocatalysts for the oxygen reduction reaction (ORR). Bimetallic core@shell nanoparticles (NPs) are widely studied nanocatalysts but often have limited lattice mismatch and surface compositions; investigations of core@shell NPs with greater compositional complexity and lattice misfit are in their infancy. Here, a new class of multimetallic NPs composed of intermetallic cores and random alloy shells is reported. Specifically, face-centered cubic (fcc) Pt- Cu random alloy shells were deposited non-epitaxially on PdCu B2 intermetallic seeds, giving rise to faceted core@shell NPs with highly strained surfaces. In fact, high resolution transmission electron microscopymore » (HRTEM) revealed orientation-dependent surface strains, where the compressive strains were minimal on Pt-Cu {111} facets but greater on {200} facets. These core@shell NPs provide higher specific and mass activities for the ORR when compared to conventional Pt-Cu NPs. Moreover, these intermetallic@random alloy NPs displayed high endurance, undergoing 10,000 cycles with only a slight decay in activity and no apparent structural changes.« less
Influence of Aluminum Passivation on the Reaction Mechanism: Flame Propagation Studies
2009-01-01
synthesis and characterization of Al nanoparticles without an oxide shell is presented in refs 15- 18. In summary, SEM, thermogravimetric analysis (TGA) and...al.1 examined the oxidation behavior of ultrafine grain aluminum powder using Rutherford back- scattering spectrometry, thermogravimetric analysis , and...to opposite predictions in nanoparticle design. The diffusion mechanism suggests that the reduction Dr complete elimination of the oxide shell will
A facile route to synthesize nanogels doped with silver nanoparticles
NASA Astrophysics Data System (ADS)
Coll Ferrer, M. Carme; Ferrier, Robert C.; Eckmann, David M.; Composto, Russell J.
2013-01-01
In this study, we describe a simple method to prepare hybrid nanogels consisting of a biocompatible core-shell polymer host containing silver nanoparticles. First, the nanogels (NG, 160 nm) containing a lysozyme rich core and a dextran rich shell, are prepared via Maillard and heat-gelation reactions. Second, silver nanoparticles (Ag NPs, 5 nm) are synthesized "in situ" in the NG solution without requiring additional reducing agents. This approach leads to stable Ag NPs located in the NG. Furthermore, we demonstrate that the amount of Ag NPs in the NG can be tuned by varying silver precursor concentration. Hybrid nanogels with silver nanoparticles have potential in antimicrobial, optical, and therapeutic applications.
Synthesis and photoluminescence of ultra-pure germanium nanoparticles
NASA Astrophysics Data System (ADS)
Chivas, R.; Yerci, S.; Li, R.; Dal Negro, L.; Morse, T. F.
2011-09-01
We have used aerosol deposition to synthesize defect and micro-strain free, ultra-pure germanium nanoparticles. Transmission electron microscopy images show a core-shell configuration with highly crystalline core material. Powder X-ray diffraction measurements verify the presence of highly pure, nano-scale germanium with average crystallite size of 30 nm and micro-strain of 0.058%. X-ray photoelectron spectroscopy demonstrates that GeO x ( x ⩽ 2) shells cover the surfaces of the nanoparticles. Under optical excitation, these nanoparticles exhibit two separate emission bands at room temperature: a visible emission at 500 nm with 0.5-1 ns decay times and an intense near-infrared emission at 1575 nm with up to ˜20 μs lifetime.
NASA Astrophysics Data System (ADS)
Mahadevan, Reena
Nanoparticles are emerging as versatile vehicles for drug delivery, providing targeting, protection, and controlled-release capabilities to encapsulated cargo. Polymeric nanoparticles made from poly(lactide-co-glycolide) (PLGA) are biodegradable, exhibit tunable drug release, and have encapsulated a wide variety of biological agents. However, PLGA nanoparticles are relatively inefficient at encapsulating small-molecule hydrophilic drugs. Liposomes encapsulate greater amounts of hydrophilic agents and demonstrate good cellular affinity; however, they lack controlled-release functionality. Hydrogel-core lipid-shell nanoparticles, or nanolipogels, combine the controlled-release capability of polymeric nanocarriers with the hydrophilic and cellular affinity of liposomes into a single drug delivery vehicle. This study establishes a facile, reproducible synthetic protocol for nanolipogels and evaluates hydrogel swelling as a mechanism for release of the small hydrophilic antiretroviral azidothymidine from nanolipogels.
Multi-walled carbon/IF-WS2 nanoparticles with improved thermal properties.
Xu, Fang; Almeida, Trevor P; Chang, Hong; Xia, Yongde; Wears, M Lesley; Zhu, Yanqiu
2013-11-07
A unique new class of core-shell structured composite nanoparticles, C-coated inorganic fullerene-like WS2 (IF-WS2) hollow nanoparticles, has been created for the first time in large quantities, by a continuous chemical vapour deposition method using a rotary furnace. Transmission electron microscopy and Raman characterisations of the resulting samples reveal that the composite nanoparticles exhibited a uniform shell of carbon coating, ranging from 2-5 nm on the IF-WS2 core, with little or no agglomeration. Importantly, thermogravimetric analysis and differential scanning calorimetry analysis confirm that their thermal stability against oxidation in air has been improved by about 70 °C, compared to the pristine IF-WS2, making these new C-coated IF-WS2 nanoparticles more attractive for critical engineering applications.
Mobasseri, Rezvan; Karimi, Mahdi; Tian, Lingling; Naderi-Manesh, Hossein; Ramakrishna, Seeram
2017-05-01
Dextran sulfate-chitosan (DS-CS) nanoparticles, which possesses properties such as nontoxicity, biocompatibility and biodegradability have been employed as drug carriers in cancer therapy. In this study, DS-CS nanoparticles were synthesized and their sizes were controlled by a modification of the divalent cations cross-linkers (Ca 2+ , Zn 2+ or Mg 2+ ). Based on the optimized processing parameters, lapatinib encapsulated nanoparticles were developed and characterized by Dynamics Light Scattering (DLS) measurements, Fourier Transform Infrared Spectroscopy (FT-IR) and Scanning Electron Microscopy (SEM). Calcium chloride (CaCl 2 ) facilitated the formation of bare (100.3±0.80nm) and drug-loaded nanoparticles (134.3±1.3nm) with narrow size distributions being the best cross-linker. The surface potential of drug-loaded nanoparticles was -16.8±0.47mV and its entrapment and loading efficiency were 76.74±1.73% and 47.36±1.27%, respectively. Cellular internalization of nanoparticles was observed by fluorescence microscopy and MTT (3-(4, 5-dimethylthiazol-2-yl)-2, 5-diphenyltetrazolium bromide) assay was used to determine cytotoxicity of bare and drug-loaded nanoparticles in comparison to the free drug lapatinib. The MTT assay showed that drug-loaded nanoparticles had comparable anticancer activity to free drug within a duration of 48h. The aforementioned results showed that the DS-CS nanoparticles were able to entrap, protect and release the hydrophobic drug, lapatinib in a controlled pattern and could further serve as a suitable drug carrier for cancer therapy. Copyright © 2016 Elsevier B.V. All rights reserved.
Varshosaz, Jaleh; Anvari, Negin
2018-06-01
Acute lymphoblastic leukemia (ALL) is the white blood cell cancer in children. L-asparaginase (L-ASNase) is one of the first drugs used in ALL treatment. Anti-tumor activity of L-ASNase is not specific and indicates limited stability in different biological environments, in addition to its quick clearance from blood. The purpose of the present study was to achieve a new L-ASNase polymer bioconjugate to improve pharmacokinetic, increase half-life and stability of the enzyme. The conjugations were achieved by the cross-linking agent of 1-ethyl-3-(3- dimethylaminopropyl) carbodiimide (EDC) which activates the carboxylic acid groups of polymeric nanoparticles to create amide bond. EDC conjugated the L-ASNase to two biodegradable polymers including; Ecoflex ® and poly (styrene-co-maleic acid) (PSMA) nanoparticles. To achieve optimal L-ASNase nanoparticles the amounts of each polymer and the crosslinker were optimized and the nanoparticles were characterized according to their particle size, zeta potential and percent of conjugation of the enzyme. The results showed that conjugated enzyme had more stability against pH changes and proteolysis. It had lower Km value (indicating more affinity to the substrate) and greater half-life in plasma and phosphate buffered saline, in comparison to native enzyme. Generally, the conjugated enzyme to PSMA nanoparticles showed greater results than Ecoflex ® nanoparticles.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Bhagat, Stuti; Srikanth Vallabani, N. V.; Shutthanandan, Vaithiyalingam
Catalytically active individual gold (Au) and cerium oxide (CeO2) nanoparticles are well known to exhibit specific enzyme-like activities, such as natural catalase, oxidase, superoxide dismutase, and peroxidase enzymes. These activities have been maneuvered to design several biological applications such as immunoassays, glucose detection, radiation and free radical protection and tissue engineering. A functional nanozyme depicting multienzyme like properties that functions as a synthetic super enzyme has eluded the researchers in the nanoscience community for past decade. In current report, we have designed a functional multienzyme in the form of Gold (core)-CeO2 (shell) nanoparticles (Au@CeO2 CSNPs) exhibiting excellent peroxidase, catalase andmore » superoxide dismutase enzyme-like activities that are controlled simply by tuning the pH. The reaction kinetic parameters reveal that the peroxidase-like activity of this core shell nanozyme is comparable to natural HRP enzyme. Unlike peroxidase-like activity exhibited by other nanomaterials, Au@CeO2 CSNPs showed decrease in hydroxyl radical formation, suggesting that the bio catalytic reactions are performed by efficient electron transfers. A significant enzyme-like activity of this core shell nanoparticle was conserved at extreme pH (2 – 11) and temperatures (up to 90 °C), clearly suggesting the superiority over natural enzymes. Further, the utility of peroxidase-like activity of this core shell nanoparticles was extended for the detection of glucose, which showed a linear range of detection between (100 µM – 1 mM). It is hypothesized that the proximity of the redox potentials of Au+/Au and Ce (III)/Ce (IV) may result in a redox couple promoting the multienzyme activity of core shell nanoparticles. Au@CeO2 CSNPs may open new directions for development of single platform sensors in multiple biosensing applications.« less
Abulateefeh, Samer R; Taha, Mutasem O
2015-01-01
Calcium alginate nanoparticles (NPs) suffer from sub-optimal stability in bio-relevant media leading to low drug encapsulation efficiency and uncontrolled release profiles. To sort out these drawbacks, a novel approach is proposed herein based on introducing tannic acid into these NPs to act as a bridging cross-linking aid agent. Calcium-alginate NPs were prepared by the ionotropic gelation method and loaded with diltiazem hydrochloride as a model drug. These NPs were characterized in terms of particle size, zeta potential, and morphology, and results were explained in accordance with Fourier-transform infrared (FTIR) spectroscopy and differential scanning calorimetry (DSC). The incorporation of tannic acid led to more than four folds increase in drug encapsulation efficiency (i.e. from 15.3% to 69.5%) and reduced burst drug release from 44% to around 10% within the first 30 min. These findings suggest the possibility of improving the properties of Ca-alginate NPs by incorporating cross-linking aid agents under mild conditions.
Composite nanoparticles containing rare earth metal and methods of preparation thereof
DOE Office of Scientific and Technical Information (OSTI.GOV)
Kandapallil, Binil Itty Ipe; Krishnan, Lakshmi; Johnson, Francis
The present invention is directed to composite nanoparticles comprising a metal, a rare earth element, and, optionally, a complexing ligand. The invention is also directed to composite nanoparticles having a core-shell structure and to processes for preparation of composite nanoparticles of the invention.
NASA Astrophysics Data System (ADS)
Xu, Chen; Zhang, Cheng; Wang, Yingxi; Li, Liu; Li, Ling; Whittaker, Andrew K.
2017-12-01
In this study, novel magnetic core-shell nanoparticles Fe3O4@La-BTC/GO have been synthesized by the layer-by-layer self-assembly (LBL) method and further modified by attachment of amino-modified PEG chains. The nanoparticles were thoroughly characterized by x-ray diffraction, FTIR, scanning electron microscopy and transmission electron microscopy. The core-shell structure was shown to be controlled by the LBL method. The drug loading of doxorubicin (DOX) within the Fe3O4@La-BTC/GO-PEG nanoparticles with different numbers of deposited layers was investigated. It was found that DOX loading increased with increasing number of metal organic framework coating layers, indicating that the drug loading can be controlled through the controllable LBL method. Cytotoxicity assays indicated that the Fe3O4@La-BTC/GO-PEG nanoparticles were biocompatible. The DOX was released rapidly at pH 3.8 and pH 5.8, but at pH 7.4 the rate and extent of release was greatly attenuated. The nanoparticles therefore demonstrate an excellent pH-triggered drug release. In addition, the particles could be tracked by magnetic resonance imaging (MRI) and fluorescence optical imaging (FOI). A clear dose-dependent contrast enhancement in T 2-weighted MR images and fluorescence images indicate the potential of these nanoparticles as dual-mode MRI/FOI contrast agents.
Sakulkhu, Usawadee; Mahmoudi, Morteza; Maurizi, Lionel; Coullerez, Geraldine; Hofmann-Amtenbrink, Margarethe; Vries, Marcel; Motazacker, Mahdi; Rezaee, Farhad; Hofmann, Heinrich
2015-02-01
As nanoparticles (NPs) are increasingly used in many applications their safety and efficient applications in nanomedicine have become concerns. Protein coronas on nanomaterials' surfaces can influence how the cell "recognizes" nanoparticles, as well as the in vitro and in vivo NPs' behaviors. The SuperParamagnetic Iron Oxide Nanoparticle (SPION) is one of the most prominent agents because of its superparamagnetic properties, which is useful for separation applications. To mimic surface properties of different types of NPs, a core-shell SPION library was prepared by coating with different surfaces: polyvinyl alcohol polymer (PVA) (positive, neutral and negative), SiO2 (positive and negative), titanium dioxide and metal gold. The SPIONs with different surfaces were incubated at a fixed serum : nanoparticle surface ratio, magnetically trapped and washed. The tightly bound proteins were quantified and identified. The surface charge has a great impact on protein adsorption, especially on PVA and silica where proteins preferred binding to the neutral and positively charged surfaces. The importance of surface material on protein adsorption was also revealed by preferential binding on TiO2 and gold coated SPION, even negatively charged. There is no correlation between the protein net charge and the nanoparticle surface charge on protein binding, nor direct correlation between the serum proteins' concentration and the proteins detected in the coronas.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Chopra, Nitin, E-mail: nchopra@eng.ua.edu; McWhinney, Hylton G.; Shi Wenwu
2011-06-15
Heterostructures composed of carbon nanotube (CNT) coated with Ni/NiO core/shell nanoparticles (denoted as CNC heterostructures) were synthesized in a wet-chemistry and single-step synthesis route involving direct nucleation of nanoparticles on CNT surface. Two different aspects of CNC heterostructures were studied here. First, it was observed that the nanoparticle coatings were more uniform on the as-produced and non-purified CNTs compared to purified (or acid treated) CNTs. These heterostructures were characterized using electron microscopy, Raman spectroscopy, and energy dispersive spectroscopy. Second, thermal stability of CNC heterostructures was studied by annealing them in N{sub 2}-rich (O{sub 2}-lean) environment between 125 and 750 deg.more » C for 1 h. A detailed X-ray photoelectron spectroscopy and Raman spectroscopy analysis was performed to evaluate the effects of annealing temperatures on chemical composition, phases, and stability of the heterostructures. It was observed that the CNTs present in the heterostructures completely decomposed and core Ni nanoparticle oxidized significantly between 600 and 750 deg. C. - Research Highlights: {yields} Heterostructures composed of CNTs coated with Ni/NiO core/shell nanoparticles. {yields} Poor nanoparticle coverage on purified CNT surface compared to non-purified CNTs. {yields} CNTs in heterostructures decompose between 600 and 750 deg. C in N{sub 2}-rich atmosphere. {yields} Metallic species in heterostructures were oxidized at higher temperatures.« less
Leong, Jun-Yee; Tey, Beng-Ti; Tan, Chin-Ping; Chan, Eng-Seng
2015-08-05
Ionotropic gelation has been an attractive method for the fabrication of biopolymeric oil-core microcapsules due to its safe and mild processing conditions. However, the mandatory use of a nozzle system to form the microcapsules restricts the process scalability and the production of small microcapsules (<100 μm). We report, for the first time, a nozzleless and surfactant-free approach to fabricate oil-core biopolymeric microcapsules through ionotropic gelation at the interface of an O/W Pickering emulsion. This approach involves the self-assembly of calcium carbonate (CaCO3) nanoparticles at the interface of O/W emulsion droplets followed by the addition of a polyanionic biopolymer into the aqueous phase. Subsequently, CaCO3 nanoparticles are dissolved by pH reduction, thus liberating Ca(2+) ions to cross-link the surrounding polyanionic biopolymer to form a shell that encapsulates the oil droplet. We demonstrate the versatility of this method by fabricating microcapsules from different types of polyanionic biopolymers (i.e., alginate, pectin, and gellan gum) and water-immiscible liquid cores (i.e., palm olein, cyclohexane, dichloromethane, and toluene). In addition, small microcapsules with a mean size smaller than 100 μm can be produced by selecting the appropriate conventional emulsification methods available to prepare the Pickering emulsion. The simplicity and versatility of this method allows biopolymeric microcapsules to be fabricated with ease by ionotropic gelation for numerous applications.
Li, Feng-Qian; Yan, Cheng; Bi, Juan; Lv, Wei-Lin; Ji, Rui-Rui; Chen, Xu; Su, Jia-Can; Hu, Jin-Hong
2011-01-01
Scopolamine hydrobromide (SH)-loaded microparticles were prepared from a colloidal fluid containing ionotropic-gelated chitosan nanoparticles using a spray-drying method. The spray-dried microparticles were then formulated into orally disintegrating tablets (ODTs) using a wet granulation tablet formation process. A drug entrapment efficiency of about 90% (w/w) and loading capacity of 20% (w/w) were achieved for the microparticles, which ranged from 2 μm to 8 μm in diameter. Results of disintegration tests showed that the formulated ODTs could be completely dissolved within 45 seconds. Drug dissolution profiles suggested that SH is released more slowly from tablets made using the microencapsulation process compared with tablets containing SH that is free or in the form of nanoparticles. The time it took for 90% of the drug to be released increased significantly from 3 minutes for conventional ODTs to 90 minutes for ODTs with crosslinked microparticles. Compared with ODTs made with noncrosslinked microparticles, it was thus possible to achieve an even lower drug release rate using tablets with appropriate chitosan crosslinking. Results obtained indicate that the development of new ODTs designed with crosslinked microparticles might be a rational way to overcome the unwanted taste of conventional ODTs and the side effects related to SH's intrinsic characteristics.
Li, Feng-Qian; Yan, Cheng; Bi, Juan; Lv, Wei-Lin; Ji, Rui-Rui; Chen, Xu; Su, Jia-Can; Hu, Jin-Hong
2011-01-01
Scopolamine hydrobromide (SH)-loaded microparticles were prepared from a colloidal fluid containing ionotropic-gelated chitosan nanoparticles using a spray-drying method. The spray-dried microparticles were then formulated into orally disintegrating tablets (ODTs) using a wet granulation tablet formation process. A drug entrapment efficiency of about 90% (w/w) and loading capacity of 20% (w/w) were achieved for the microparticles, which ranged from 2 μm to 8 μm in diameter. Results of disintegration tests showed that the formulated ODTs could be completely dissolved within 45 seconds. Drug dissolution profiles suggested that SH is released more slowly from tablets made using the microencapsulation process compared with tablets containing SH that is free or in the form of nanoparticles. The time it took for 90% of the drug to be released increased significantly from 3 minutes for conventional ODTs to 90 minutes for ODTs with crosslinked microparticles. Compared with ODTs made with noncrosslinked microparticles, it was thus possible to achieve an even lower drug release rate using tablets with appropriate chitosan crosslinking. Results obtained indicate that the development of new ODTs designed with crosslinked microparticles might be a rational way to overcome the unwanted taste of conventional ODTs and the side effects related to SH’s intrinsic characteristics. PMID:21720502
Duchstein, Patrick; Milek, Theodor; Zahn, Dirk
2015-01-01
Molecular models of 5 nm sized ZnO/Zn(OH)2 core-shell nanoparticles in ethanolic solution were derived as scale-up models (based on an earlier model created from ion-by-ion aggregation and self-organization) and subjected to mechanistic analyses of surface stabilization by block-copolymers. The latter comprise a poly-methacrylate chain accounting for strong surfactant association to the nanoparticle by hydrogen bonding and salt-bridges. While dangling poly-ethylene oxide chains provide only a limited degree of sterical hindering to nanoparticle agglomeration, the key mechanism of surface stabilization is electrostatic shielding arising from the acrylates and a halo of Na+ counter ions associated to the nanoparticle. Molecular dynamics simulations reveal different solvent shells and distance-dependent mobility of ions and solvent molecules. From this, we provide a molecular rationale of effective particle size, net charge and polarizability of the nanoparticles in solution.
Duchstein, Patrick; Milek, Theodor; Zahn, Dirk
2015-01-01
Molecular models of 5 nm sized ZnO/Zn(OH)2 core-shell nanoparticles in ethanolic solution were derived as scale-up models (based on an earlier model created from ion-by-ion aggregation and self-organization) and subjected to mechanistic analyses of surface stabilization by block-copolymers. The latter comprise a poly-methacrylate chain accounting for strong surfactant association to the nanoparticle by hydrogen bonding and salt-bridges. While dangling poly-ethylene oxide chains provide only a limited degree of sterical hindering to nanoparticle agglomeration, the key mechanism of surface stabilization is electrostatic shielding arising from the acrylates and a halo of Na+ counter ions associated to the nanoparticle. Molecular dynamics simulations reveal different solvent shells and distance-dependent mobility of ions and solvent molecules. From this, we provide a molecular rationale of effective particle size, net charge and polarizability of the nanoparticles in solution. PMID:25962096
Yan, Mina; Zhang, Zhaoguo; Cui, Shengmiao; Lei, Ming; Zeng, Ke; Liao, Yunhui; Chu, Weijing; Deng, Yihui; Zhao, Chunshun
2014-01-01
Layered double hydroxide (LDH) has attracted considerable attention as a drug carrier. However, because of its poor in vivo behavior, polyethylene glycolylated (PEGylated) phospholipid must be used as a coformer to produce self-assembled core–shell nanoparticles. In the present study, we prepared a PEGylated phospholipid-coated LDH (PLDH) (PEG-PLDH) delivery system. The PEG-PLDH nanoparticles had an average size of 133.2 nm. Their core–shell structure was confirmed by transmission electron microscopy and X-ray photoelectron spectroscopy. In vitro liposome-cell-association and cytotoxicity experiments demonstrated its ability to be internalized by cells. In vivo studies showed that PEGylated phospholipid membranes greatly reduced the blood clearance rate of LDH nanoparticles. PEG-PLDH nanoparticles demonstrated a good control of tumor growth and increased the survival rate of mice. These results suggest that PEG-PLDH nanoparticles can be a useful drug delivery system for cancer therapy. PMID:25364245
Wang, Guan; Zhang, Kai; Wang, Yindian; Zhao, Changwen; He, Bin; Ma, Yuhong; Yang, Wantai
2018-05-03
Surface engineering of individual living cells is a promising field for cell-based applications. However, engineering individual cells with controllable thickness by chemical methods has been rarely studied. This article describes the development of a new cytocompatible chemical strategy to decorate individual living cells. The thicknesses of the crosslinked shells could be conveniently controlled by the irradiation time, visible light intensity, or monomer concentration. Moreover, the lag phase of the yeast cell division was extended and their stability against lysis was improved, which could also be tuned by controlling the shell thickness.
NASA Astrophysics Data System (ADS)
Zhu, Jian; Chang, Hui; Li, Jian-Jun; Li, Xin; Zhao, Jun-Wu
2018-01-01
The effect of silicon-coated gold nanoparticles with different gold core diameter and silica shell thickness on the fluorescence emission of CdTe quantum dots (QDs) was investigated. For gold nanoparticles with a diameter of 15 nm, silica coating can only results in fluorescence recover of the bare gold nanoparticle-induced quenching of QDs. However, when the size of gold nanoparticle is increased to 60 nm, fluorescence enhancement of the QDs could be obtained by silica coating. Because of the isolation of the silica shell-reduced quenching effect and local electric field effect, the fluorescence of QDs gets intense firstly and then decreases. The maximum fluorescence enhancement takes place as the silica shell has a thickness of 30 nm. This enhanced fluorescence from silicon-coated gold nanoparticles is demonstrated for sensing of Hg2 +. Under optimal conditions, the enhanced fluorescence intensity decreases linearly with the concentration of Hg2 + ranging from 0 to 200 ng/mL. The limit of detection for Hg2 + is 1.25 ng/mL. Interference test and real samples detection indicate that the influence from other metal ions could be neglected, and the Hg2 + could be specifically detected.
NASA Astrophysics Data System (ADS)
Körpe, Didem Aksoy; Malekghasemi, Soheil; Aydın, Uğur; Duman, Memed
2014-12-01
Biopolymers such as chitosan and alginate are widely used for controlled drug delivery systems. The present work aimed to develop a new protocol for preparation of monodisperse alginate-coated chitosan nanoparticles at nanoscale. Modifications of preparation protocol contain changing the pH of polymer solutions and adding extra centrifugation steps into the procedure. While chitosan nanoparticles were synthesized by ionic gelation method, they were coated with alginate by electrostatic interaction. The size, morphology, charge, and structural characterization of prepared core-shell nanoparticulated system were performed by AFM, Zeta sizer, and FTIR. BSA and DOX were loaded as test biomolecules to core and shell part of the nanoparticle, respectively. Release profiles of BSA and DOX were determined by spectrophotometry. The sizes of both chitosan and alginate-coated chitosan nanoparticles which were prepared by modified protocol were measured to be 50 ± 10 and 60 ± 3 nm, respectively. After loading BSA and DOX, the average size of the particles increased to 80 ± 7 nm. Moreover, while the zeta potential of chitosan nanoparticles was positive value, the value was inverted to negative after alginate coating. Release profile measurements of BSA and DOX were determined during 57 and 2 days, respectively. Our results demonstrated that monodisperse alginate-coated nanoparticles were synthesized and loaded successfully using our modified protocol.
NASA Astrophysics Data System (ADS)
Zhang, Zhaohui; Liu, Li; Li, Hui; Yao, Shouzhuo
2009-09-01
A novel core-shell molecularly imprinting microspheres (MIMs) with trans-resveratrol as the template molecule; acrylamide (AA) as functional monomer and ethylene glycol dimethacrylate (EGDMA) as cross-linker, was prepared based on SiO 2 microspheres with surface imprinting technique. These core-shell trans-resveratrol imprinted microspheres were characterized by infrared spectra (IR), scanning electron microscopy (SEM), thermogravimetric analysis (TGA), and high performance liquid chromatography (HPLC). The results showed that these core-shell imprinted microspheres, which take on perfect spherical shape with average shell thickness of 150 nm, exhibit especially selective recognition for trans-resveratrol. These imprinted microspheres were applied as solid-phase extraction materials for selective extraction of trans-resveratrol from giant knotweed extracting solution successfully.
NASA Astrophysics Data System (ADS)
Hill, Laura E.; Gomes, Carmen L.
2014-09-01
Chitosan and alginate are both pH-responsive biopolymers extracted from crustacean exoskeletons and brown algae, respectively. Poly-N-isopropylacrylamide (PNIPAAM) is a hydrogel that becomes hydrophobic at a lower-critical solution temperature. This study sought to combine pH- and temperature-responsive polymers via crosslinking, in order to create a dual-stimuli responsive polymer for hydrophobic antimicrobial compounds delivery, improving their antimicrobial effects. Cinnamon bark extract (CBE) was used as a model for hydrophobic antimicrobial. Two co-polymers were synthesized to create two nanoparticles types: chitosan-co-PNIPAAM and alginate-co-PNIPAAM. Nanoparticles were formed from the resulting co-polymers using a self-assembly top-down process followed by glutaraldehyde or calcium chloride crosslinking. These nanoparticles were then used as controlled delivery vehicles for CBE, whose rapid release could be triggered by specific external stimuli. For the same pH and temperature conditions, the chitosan-co-PNIPAAM nanoparticles were significantly more potent bacterial inhibitors against both pathogens and also exhibited a faster CBE release over time as well as slightly higher entrapment efficiency. The alginate-co-PNIPAAM nanoparticles were significantly smaller and exhibited a slow, gradual release over a long time period. Although both nanoparticles were able to effectively inhibit pathogen growth at lower (P < 0.05) concentration than free CBE, the chitosan-co-PNIPAAM nanoparticles were more effective in delivering a natural antimicrobial with controlled release against foodborne pathogens.
DOE Office of Scientific and Technical Information (OSTI.GOV)
Lee, Li -Chen; Lu, Jie; Weck, Marcus
In shell cross-linked micelles (SCMs) containing acid sites in the shell and base sites in the core are prepared from amphiphilic poly(2-oxazoline) triblock copolymers. These materials are utilized as two-chamber nanoreactors for a prototypical acid-base bifunctional tandem deacetalization-nitroaldol reaction. Furthermore, the acid and base sites are localized in different regions of the micelle, allowing the two steps in the reaction sequence to largely proceed in separate compartments, akin to the compartmentalization that occurs in biological systems.