cover pictures Fluorescent Nanodiamonds The cover image is a pop art representation of a shell architecture on fluorescent nanodiamond. As P. Cigler and co-workers report on page 1106, the diamond nanoparticle is embedded in a silica shell, which is terminated by a hydrophillic, azide- or alkyne-substituted PEG polymer. In contrast to unmodified nanodiamonds, this nanoarchitecture brings high colloidal stability in buffers and biological media and the possibility to modify the particles by biomolecules in high yields using click chemistry.
Intracellular Drug Delivery A supramolecular peptide-amphiphile system (SPAS) based on peptide dendrimers and linear peptides is reported on page 1133 by Z. Gu and co-workers. As shown in the Taiji Diagram, the SPAS have a well-defined nanostructure at pH 7.4, but the whole SPAS system disassembles at pH 6.2. This pH-dependent process is attributed to the polyelectrolyte property of peptides causing the formation and disappearance of weak interactions in non-covalent dendritic peptide-amphiphiles. This SPAS is explored as a smart drug nanovehicle to encapsulate anticancer drugs at normal physiological conditions, and it can disassemble to release the drugs at the pH levels found inside tumor cells.
Microcapsules Osmocapsules are microfluidically created to provide a tool for direct measurement of osmotic pressure. As reported by S.-H. Kim and co-workers on page 1155, the osmocapsules enclose standard aqueous solution with an ultrathin polymeric membrane. When many distinct osmocapsules with all different osmolarities are dispersed in an unknown solution, the osmocapsules, subjected to positive osmotic pressure, selectively exhibit discernible buckling. In the image, only red and orange capsules buckle, whereas yellow and green do not. This enables the estimation of osmotic pressure of the medium, which is in a range between the osmotic pressures of aqueous cores of orange and yellow capsules.
Y. T. Zhang, W. F. Ma, D. Li, M. Yu, J. Guo, C. C. Wang* Benzoboroxole-Functionalized Magnetic Core/Shell Microspheres for Highly Specific Enrichment of Glycoproteins under Physiological Conditions DOI: 10.1002/smll.201302841
small 2014, 10, No. 6, 1031
J. H. Kim, D. H. Nam, Y. W. Lee, Y. S. Nam,* C. B. Park* Self-Assembly of Metalloporphyrins into Light-Harvesting Peptide Nanofiber Hydrogels for Solar Water Oxidation DOI: 10.1002/smll.201302627
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Look for these important papers in upcoming issues of Small or at www.small-journal.com All our articles are available online in advance of print. The articles listed here have been judged by either the referees or the editor to be very important, and were immediately copyedited, proofread, and published online. As long as there is no page number available, online manuscripts should be cited in the following manner: Authors, Small, online publication date, DOI number.
www.small-journal.com
1031
contents
review Graphene
Understanding the behavior of monolayer and sub-monolayer films of molecules on graphene is critical to controlling the growth of these films, and exploiting them for doping, bandgap engineering, and for yet unforeseen applications. Here, the recent progress towards understanding molecular selfassembly on graphene is reviewed.
J. M. MacLeod,* F. Rosei* __ 1038–1049 Molecular Self-Assembly on Graphene
communications Light-Emitting Materials
A light-emitting diode is fabricated and characterized on a semiconducting serpentine CNT which has many parallel segments with identical chirality. Compared with the individual CNT and CNT-film devices, the device with parallel segments shows improvement of an order of magnitude in current, significantly larger electroluminescent intensity, and narrower emission bands. Serpentine nanotubes are an ideal choice for practical applications of CNT-based light sources.
D. M. Yu, S. Wang,* L. H. Ye, W. Li, Z. Y. Zhang, Y. B. Chen, J. Zhang, L.-M. Peng* ______________ 1050–1056 Electroluminescence from Serpentine Carbon Nanotube Based Light-Emitting Diodes on Quartz
DNA Origami
The self-assembly of silver nanoparticles into a bow-tie antenna configuration is achieved with the DNA origami method. Instead of complicated particle geometries, spherical silver nanoparticles are used. Formation of the structures in high yields is verified with transmission electron microscopy and agarose gel electrophoresis. According to finite-difference time-domain simulations, the antenna configuration could be used as a DNA sensor.
A.-P. Eskelinen, R. J. Moerland, M. A. Kostiainen, P. Törmä* ___1057–1062 Self-Assembled Silver Nanoparticles in a Bow-Tie Antenna Configuration
Polypyrrole Nanoparticles
Magnetic Fe3O4 crystals are produced in situ on preformed polypyrrole (PPY) nanoparticles by rationally converting the residual Fe species in the synthetic system. The obtained PPY@Fe3O4 composite nanoparticles exhibit good photostability and biocompatibility, and they can be used as multifunctional probes for MRI, thermal imaging, and photothermal ablation of cancer cells.
Q. W. Tian, Q. Wang, K. X. Yao, B. Y. Teng, J. Z. Zhang, S. P. Yang, Y. Han* _________________ 1063–1068 Multifunctional Polypyrrole@Fe3O4 Nanoparticles for Dual-Modal Imaging and In Vivo Photothermal Cancer Therapy
1032 www.small-journal.com
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
small 2014, 10, No. 6, 1032–1037
Interaction between hydrophobic nanoparticles (NPs) and a pulmonary surfactant (PS) film leads to a shift in molecular packing of surfactant molecules in the PS film around the interacting NPs. The resultant structural arrangement of surfactants around the NPs may be a potential structural factor responsible for their high retention ability within the film. Moreover, during this interaction, surfactant molecules coat the NPs and change their surface properties.
Surface Interactions
Microreactors are an emerging technology for the controlled synthesis of nanoparticles. The Multi-Temperature zone Microreactor (MTM) described in this work utilizes thermally isolated heated and cooled regions for the purpose of separating nucleation and growth processes as well as to provide a platform for a systematic study on the effect of reaction conditions on nanoparticle synthesis.
Microfluidics
A. K. Sachan,* H.-J. Galla ___ 1069–1075 Understanding the Mutual Impact of Interaction between Hydrophobic Nanoparticles and Pulmonary Surfactant Monolayer
E. Y. Erdem,* J. C. Cheng, F. M Doyle, A. P. Pisano ______________ 1076–1080 Multi-Temperature Zone, Droplet-based Microreactor for Increased Temperature Control in Nanoparticle Synthesis
A controlled magnetic field creates patterns of superparamagnetic nanoparticles with a minimum line width of 10 μm on a flexible substrate. This magnetic printing method is also successfully used to print conductive patterns consisting of copper or carbon nanomaterials.
Self-Assembly T. Ahn, S. Oh, X. Hu, J. W. Lee, C. W. Park, H.-M. Yang, C. Kim, J.-D. Kim* ________________1081–1085 Controlled Self-Assembly for High-Resolution Magnetic Printing
A new ELISA- (enzyme-linked immunosorbent assay)-like assay is demonstrated in which no elements of biological origin are used for molecular recognition or signaling. Composite imprinted nanoparticles that contain a catalytic core and which are synthesized by using a solid-phase approach can simultaneously act as recognition/signaling elements, and be used with minimal modifications to standard assay protocols. This assay provides a new route towards replacement of unstable biomolecules in immunoassays.
Molecular Recognition R. V. Shutov, A. Guerreiro,* E. Moczko, I. Perez de Vargas-Sansalvador, I. Chianella, M. J. Whitcombe, S. A. Piletsky_____________ 1086–1089 Introducing MINA – The Molecularly Imprinted Nanoparticle Assay
small 2014, 10, No. 6, 1032–1037
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.small-journal.com
1033
contents SERS
Though the SERS effect based on pristine MoS2 is hardly observed, however, the plasma treated MoS2 nanoflakes can be used as an ideal substrate for surface enhanced Raman scattering. It is proved that the structural disorder induced generation of local dipoles and adsorption of oxygen on the plasma treated MoS2 nanosheets are the two basic and important driven forces for the enhancement of Raman signals of surface adsorbed R6G molecules.
L. F. Sun, H. L. Hu, D. Zhan,* J. X. Yan, L. Liu, J. S. Teguh, E. K. L. Yeow, P. S. Lee, Z. X. Shen* ______ 1090–1095 Plasma Modified MoS2 Nanoflakes for Surface Enhanced Raman Scattering
Batteries
Single-crystalline LiMn2O4 hollow nanocones are synthesized via a template-engaged low-temperature lithiation reaction. When applied as cathode materials for lithium-ion batteries, they can deliver a high specific capacity of 127.1 mAh g-1 at 0.1 C and the capacity still maintains 100 mAh g-1 even at 50 °C. After over 1000 cycles at 5 °C, 94.8% of the initial capacity is retained.
H. Jiang, Y. Fu, Y. Hu, C. Yan, L. Zhang, P. S. Lee,* C. Z. Li* ________ 1096–1100 Hollow LiMn2O4 Nanocones as Superior Cathode Materials for Lithium-Ion Batteries with Enhanced Power and Cycle Performances
Biosensors
Label-free MoS2 nanosheet-based fieldeffect biosensor detects cancer marker protein Prostate Specific Antigen in real time with high sensitivity and selectivity, exhibiting great potential in point-of-care diagnostics application.
L. Wang, Y. Wang, J. I. Wong, T. Palacios, J. Kong, H. Y. Yang*_________ 1101–1105 Functionalized MoS2 Nanosheet-Based Field-Effect Biosensor for Label-Free Sensitive Detection of Cancer Marker Proteins in Solution
full papers Biocompatible non-photobleachable fluorescent nanoprobes are prepared from nanodiamonds containing nitrogen-vacancy centers. The translucent, near-spherical shell architecture enables quick and highly effective decoration of particles with various (bio)molecules using click chemistry. The particles show superior behavior in cell experiments and they fully exploit the unique photophysical properties of nitrogen-vacancy centers.
Fluorescent Nanodiamonds I. Rehor, J. Slegerova, J. Kucka, V. Proks, V. Petrakova, M.-P. Adam, F. Treussart, S. Turner, S. Bals, P. Sacha, M. Ledvina, A. M. Wen, N. F. Steinmetz, P. Cigler* _________________ 1106–1115 Fluorescent Nanodiamonds Embedded in Biocompatible Translucent Shells
1034 www.small-journal.com
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
small 2014, 10, No. 6, 1032–1037
The gadolinium chelate coated gold nanoparticles (Au@DTDTPA-Gd50) which were designed as contrast agents for magnetic resonance imaging (MRI) also behave as radiosensitizers. Their followup by MRI allows determining the delay between the irradiation of the tumor and the injection of the nanoparticles. As a result, the use of Au@DTDTPA-Gd50 nanoparticles leads to the improvement of the effect of radiotherapy.
Contrast Agents
Doped small-molecule organic nanoparticles (NPs) are used in a new strategy to achieve excellent fluorescent probes with high brightness, large Stokes shifts and tunable emissions for in vitro and in vivo imaging. The results indicate that doped NPs obtained by this strategy are promising as a fluorescent probe in biomedical applications.
Fluorescent Nanoparticles
I. Miladi, C. Alric, S. Dufort, P. Mowat, A. Dutour, C. Mandon, G. Laurent, E. Bräuer-Krisch, N. Herath, J.-L. Coll, M. Dutreix, F. Lux, R. Bazzi, C. Billotey, M. Janier, P. Perriat, G. L. Duc,* S. Roux,* O. Tillement ______________ 1116–1124 The In Vivo Radiosensitizing Effect of Gold Nanoparticles Based MRI Contrast Agents
J. Yu, X. J. Diao, X. J. Zhang,* X. F. Chen, X. J. Hao, W. Li, X. H. Zhang,* C.-S. Lee* ________________ 1125–1132 Water-Dispersible, pH-Stable and Highly-Luminescent Organic Dye Nanoparticles with Amplified Emissions for In Vitro and In Vivo Bioimaging
A smart nanovehicle for use as a novel drug nanocarrier is designed based on a supramolecular peptide-amphiphile system (SPAS). SPAS exists as a welldefined nanostructure at pH 7.4, but the whole SPAS system disassembles at pH 6.2. Because SPAS can encapsulate anticancer drugs at normal physiological conditions, and it can disassemble to release the drug at the pH levels found inside tumor cells.
Intracellular Drug Delivery
The future achievement of depth tissue real in vivo imaging requires the development of novel efficient infrared fluorescence nanoparticles. In this work, the potential application of Nd3+-doped LaF3 nanoparticles is reported for fluorescence bioimaging based on their three main emission channels of Nd3+ ions (first and second biological windows). High contrast and low toxicity are obtained, both in vivo and in vitro, using 1.06 μm.
Bioimaging
small 2014, 10, No. 6, 1032–1037
X. Xu, Y. Li, H. Li, R. Liu, M. Sheng, B. He, Z. Gu* ______________ 1133–1140 Smart Nanovehicles Based on pH-Triggered Disassembly of Supramolecular Peptide-Amphiphiles for Efficient Intracellular Drug Delivery
U. Rocha, K. U. Kumar, C. Jacinto, I. Villa, F. Sanz-Rodríguez, M. del Carmen Iglesias de la Cruz, A. Juarranz, E. Carrasco, F. C. J. M. van Veggel, E. Bovero, J. G. Solé, D. Jaque* _________1141–1154 Neodymium-Doped LaF3 Nanoparticles for Fluorescence Bioimaging in the Second Biological Window
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.small-journal.com
1035
contents Osmocapsules are synthesized to provide tools for the direct measurement of osmotic pressure. Double-emulsion drops with an ultra-thin shell serve as templates to prepare microcapsules containing standard osmotic strength. The osmocapsules, subjected to positive osmotic pressure, exhibit discernible buckling, thereby enabling the measurement of the pressure. Moreover, these injectable osmocapsules are potentially useful for in-vivo pressure measurements and triggered release of drugs.
Microcapsules S.-H. Kim,* T. Y. Lee, S. S. Lee _________________ 1155–1162 Osmocapsules for Direct Measurement of Osmotic Strength
Quantum Dots
The coating dynamics of nanocrystal micelles is studied by monitoring in situ the energy transfer from quantum dot core to dye-labeled lipids. The dependences of lipid exchange on concentration, temperature and solvent are investigated. Exchange rate constant and activation energy are determined by fitting the results.
Y. Zhao, P. Schapotschnikow, T. Skajaa, T. J. H. Vlugt, W. J. M. Mulder, C. de Mello Donegá, A. Meijerink* _____________ 1163–1170 Probing Lipid Coating Dynamics of Quantum Dot Core Micelles via Förster Resonance Energy Transfer
MgO Nanoparticles Y. H. Leung, A. M. C. Ng, X. Xu, Z. Shen, L. A. Gethings, M. T. Wong, C. M. N. Chan, M. Y. Guo, Y. H. Ng, A. B. Djurišic´,* P. K. H. Lee,* W. K. Chan, L. H. Yu, D. L. Phillips, A. P. Y. Ma, F. C. C. Leung _____________ 1171–1183
Robust antibacterial activity on Escherichia coli cells in the absence of ROS production is demonstrated. Multiple lines of evidence clearly show the absence of oxidative stress and indicate that the primary mechanism of cell death is related to cell membrane damage, which does not appear to be due to lipid peroxidation.
Mechanisms of Antibacterial Activity of MgO: Non-ROS Mediated Toxicity of MgO Nanoparticles Towards Escherichia coli
Self-Assembly E. Huynh, J. F. Lovell, R. Fobel, G. Zheng* ________________1184–1193
Micrometer-sized vesicles generated from a porphyrin-lipid bilayer demonstrate the ability to induce membrane permeability, forming a large pore which then self-seals upon laser irradiation. The precise control associated with this technique allows a variety of microreactor applications such as DNA hybridization and enzyme reactions.
Optically Controlled Pore Formation in Self-Sealing Giant Porphyrin Vesicles
1036 www.small-journal.com
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
small 2014, 10, No. 6, 1032–1037
The influence of ligand anchor and bridging groups on the optical and electronic properties of pyrite nanocrystal thin films is investigated systematically. The thin film absorption onset shifts up to 100 meV to the red and the differential conductance varies over four orders of magnitude for the different ligands with ammonium sulfides and thiolated aromatic linkers showing the largest effects.
Semiconductor Nanocrystals
Magnetic (bMR) nanosensors are used to screen a library of small molecules for binding to and inhibition of the Anthrax lethal factor (LF). Out of 30 different bMR nanosensors, only two, containing sulindac and fusaric acid on their surfaces, were able to inhibit the protease activity of LF. Meanwhile, the sulindac bMR nanosensor by itself was a potent inhibitor of LF macrophage cytoxocity with an IC50 in the low nanomolar range.
Magnetic Nanosensors
Single-chain conjugated polymer (CP) dots embedded nanoparticles (NPs) are fabricated via encapsulation method by optimization of CP and matrix feed concentrations. DSPE-PEG-Maleimide as the polymer matrix endows NPs with surface maleimide groups, which favours easy conjugation with TAT peptide via click chemistry to pres erve its biofunctions. The obtained CPNPs show high brightness and good biocompatibility, which allow cell tracing for over 9 generations, superior to commercial cell tracker Qtracker 585.
Conjugated Polymers
W. Li, T. Dittrich,* F. Jäckel,* J. Feldmann* ______________1194–1201 Optical and Electronic Properties of Pyrite Nanocrystal Thin Films: the Role of Ligands
O. J. Santiesteban, C. Kaittanis, J. M. Perez* _______________1202–1211 Identification of Toxin Inhibitors Using a Magnetic Nanosensor-Based Assay
G. Feng, K. Li, J. Liu, D. Ding, B. Liu* ___________________ 1212–1219 Bright Single-Chain Conjugated Polymer Dots Embedded Nanoparticles for Long-Term Cell Tracing and Imaging
Nanoshell on nanocapsule: Surface seeding method constructs gold nanoshell on liquid perfluorocarbon nanocapsules, giving the echogenic contrast agent extra functionalities of CT contrast enhancement and photo-induced hyperthermia therapy. The nanocapsule theranostic agent is demonstrated to utilize combined dual modal ultrasound/CT contrast imaging and photothermal tumor ablation, which may have potential impact on methodology of cancer diagnosis and therapy.
Nanomedicine H. Ke, X. Yue, J. Wang, S. Xing, Q. Zhang, Z. Dai,* J. Tian,* S. Wang, Y. Jin ____________ 1220–1227 Gold Nanoshelled Liquid Perfluorocarbon Nanocapsules for Combined Dual Modal Ultrasound/CT Imaging and Photothermal Therapy of Cancer
small 2014, 10, No. 6, 1032–1037
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.small-journal.com
1037
Intracellular Drug Delivery A supramolecular peptide-amphiphile system (SPAS) based on peptide dendrimers and linear peptides is reported on page 1133 by Z. Gu and co-workers. As shown in the Taiji Diagram, the SPAS have a well-defined nanostructure at pH 7.4, but the whole SPAS system disassembles at pH 6.2. This pH-dependent process is attributed to the polyelectrolyte property of peptides causing the formation and disappearance of weak interactions in non-covalent dendritic peptide-amphiphiles. This SPAS is explored as a smart drug nanovehicle to encapsulate anticancer drugs at normal physiological conditions, and it can disassemble to release the drugs at the pH levels found inside tumor cells.
Microcapsules Osmocapsules are microfluidically created to provide a tool for direct measurement of osmotic pressure. As reported by S.-H. Kim and co-workers on page 1155, the osmocapsules enclose standard aqueous solution with an ultrathin polymeric membrane. When many distinct osmocapsules with all different osmolarities are dispersed in an unknown solution, the osmocapsules, subjected to positive osmotic pressure, selectively exhibit discernible buckling. In the image, only red and orange capsules buckle, whereas yellow and green do not. This enables the estimation of osmotic pressure of the medium, which is in a range between the osmotic pressures of aqueous cores of orange and yellow capsules.
Y. T. Zhang, W. F. Ma, D. Li, M. Yu, J. Guo, C. C. Wang* Benzoboroxole-Functionalized Magnetic Core/Shell Microspheres for Highly Specific Enrichment of Glycoproteins under Physiological Conditions DOI: 10.1002/smll.201302841
small 2014, 10, No. 6, 1031
J. H. Kim, D. H. Nam, Y. W. Lee, Y. S. Nam,* C. B. Park* Self-Assembly of Metalloporphyrins into Light-Harvesting Peptide Nanofiber Hydrogels for Solar Water Oxidation DOI: 10.1002/smll.201302627
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Look for these important papers in upcoming issues of Small or at www.small-journal.com All our articles are available online in advance of print. The articles listed here have been judged by either the referees or the editor to be very important, and were immediately copyedited, proofread, and published online. As long as there is no page number available, online manuscripts should be cited in the following manner: Authors, Small, online publication date, DOI number.
www.small-journal.com
1031
contents
review Graphene
Understanding the behavior of monolayer and sub-monolayer films of molecules on graphene is critical to controlling the growth of these films, and exploiting them for doping, bandgap engineering, and for yet unforeseen applications. Here, the recent progress towards understanding molecular selfassembly on graphene is reviewed.
J. M. MacLeod,* F. Rosei* __ 1038–1049 Molecular Self-Assembly on Graphene
communications Light-Emitting Materials
A light-emitting diode is fabricated and characterized on a semiconducting serpentine CNT which has many parallel segments with identical chirality. Compared with the individual CNT and CNT-film devices, the device with parallel segments shows improvement of an order of magnitude in current, significantly larger electroluminescent intensity, and narrower emission bands. Serpentine nanotubes are an ideal choice for practical applications of CNT-based light sources.
D. M. Yu, S. Wang,* L. H. Ye, W. Li, Z. Y. Zhang, Y. B. Chen, J. Zhang, L.-M. Peng* ______________ 1050–1056 Electroluminescence from Serpentine Carbon Nanotube Based Light-Emitting Diodes on Quartz
DNA Origami
The self-assembly of silver nanoparticles into a bow-tie antenna configuration is achieved with the DNA origami method. Instead of complicated particle geometries, spherical silver nanoparticles are used. Formation of the structures in high yields is verified with transmission electron microscopy and agarose gel electrophoresis. According to finite-difference time-domain simulations, the antenna configuration could be used as a DNA sensor.
A.-P. Eskelinen, R. J. Moerland, M. A. Kostiainen, P. Törmä* ___1057–1062 Self-Assembled Silver Nanoparticles in a Bow-Tie Antenna Configuration
Polypyrrole Nanoparticles
Magnetic Fe3O4 crystals are produced in situ on preformed polypyrrole (PPY) nanoparticles by rationally converting the residual Fe species in the synthetic system. The obtained PPY@Fe3O4 composite nanoparticles exhibit good photostability and biocompatibility, and they can be used as multifunctional probes for MRI, thermal imaging, and photothermal ablation of cancer cells.
Q. W. Tian, Q. Wang, K. X. Yao, B. Y. Teng, J. Z. Zhang, S. P. Yang, Y. Han* _________________ 1063–1068 Multifunctional Polypyrrole@Fe3O4 Nanoparticles for Dual-Modal Imaging and In Vivo Photothermal Cancer Therapy
1032 www.small-journal.com
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
small 2014, 10, No. 6, 1032–1037
Interaction between hydrophobic nanoparticles (NPs) and a pulmonary surfactant (PS) film leads to a shift in molecular packing of surfactant molecules in the PS film around the interacting NPs. The resultant structural arrangement of surfactants around the NPs may be a potential structural factor responsible for their high retention ability within the film. Moreover, during this interaction, surfactant molecules coat the NPs and change their surface properties.
Surface Interactions
Microreactors are an emerging technology for the controlled synthesis of nanoparticles. The Multi-Temperature zone Microreactor (MTM) described in this work utilizes thermally isolated heated and cooled regions for the purpose of separating nucleation and growth processes as well as to provide a platform for a systematic study on the effect of reaction conditions on nanoparticle synthesis.
Microfluidics
A. K. Sachan,* H.-J. Galla ___ 1069–1075 Understanding the Mutual Impact of Interaction between Hydrophobic Nanoparticles and Pulmonary Surfactant Monolayer
E. Y. Erdem,* J. C. Cheng, F. M Doyle, A. P. Pisano ______________ 1076–1080 Multi-Temperature Zone, Droplet-based Microreactor for Increased Temperature Control in Nanoparticle Synthesis
A controlled magnetic field creates patterns of superparamagnetic nanoparticles with a minimum line width of 10 μm on a flexible substrate. This magnetic printing method is also successfully used to print conductive patterns consisting of copper or carbon nanomaterials.
Self-Assembly T. Ahn, S. Oh, X. Hu, J. W. Lee, C. W. Park, H.-M. Yang, C. Kim, J.-D. Kim* ________________1081–1085 Controlled Self-Assembly for High-Resolution Magnetic Printing
A new ELISA- (enzyme-linked immunosorbent assay)-like assay is demonstrated in which no elements of biological origin are used for molecular recognition or signaling. Composite imprinted nanoparticles that contain a catalytic core and which are synthesized by using a solid-phase approach can simultaneously act as recognition/signaling elements, and be used with minimal modifications to standard assay protocols. This assay provides a new route towards replacement of unstable biomolecules in immunoassays.
Molecular Recognition R. V. Shutov, A. Guerreiro,* E. Moczko, I. Perez de Vargas-Sansalvador, I. Chianella, M. J. Whitcombe, S. A. Piletsky_____________ 1086–1089 Introducing MINA – The Molecularly Imprinted Nanoparticle Assay
small 2014, 10, No. 6, 1032–1037
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.small-journal.com
1033
contents SERS
Though the SERS effect based on pristine MoS2 is hardly observed, however, the plasma treated MoS2 nanoflakes can be used as an ideal substrate for surface enhanced Raman scattering. It is proved that the structural disorder induced generation of local dipoles and adsorption of oxygen on the plasma treated MoS2 nanosheets are the two basic and important driven forces for the enhancement of Raman signals of surface adsorbed R6G molecules.
L. F. Sun, H. L. Hu, D. Zhan,* J. X. Yan, L. Liu, J. S. Teguh, E. K. L. Yeow, P. S. Lee, Z. X. Shen* ______ 1090–1095 Plasma Modified MoS2 Nanoflakes for Surface Enhanced Raman Scattering
Batteries
Single-crystalline LiMn2O4 hollow nanocones are synthesized via a template-engaged low-temperature lithiation reaction. When applied as cathode materials for lithium-ion batteries, they can deliver a high specific capacity of 127.1 mAh g-1 at 0.1 C and the capacity still maintains 100 mAh g-1 even at 50 °C. After over 1000 cycles at 5 °C, 94.8% of the initial capacity is retained.
H. Jiang, Y. Fu, Y. Hu, C. Yan, L. Zhang, P. S. Lee,* C. Z. Li* ________ 1096–1100 Hollow LiMn2O4 Nanocones as Superior Cathode Materials for Lithium-Ion Batteries with Enhanced Power and Cycle Performances
Biosensors
Label-free MoS2 nanosheet-based fieldeffect biosensor detects cancer marker protein Prostate Specific Antigen in real time with high sensitivity and selectivity, exhibiting great potential in point-of-care diagnostics application.
L. Wang, Y. Wang, J. I. Wong, T. Palacios, J. Kong, H. Y. Yang*_________ 1101–1105 Functionalized MoS2 Nanosheet-Based Field-Effect Biosensor for Label-Free Sensitive Detection of Cancer Marker Proteins in Solution
full papers Biocompatible non-photobleachable fluorescent nanoprobes are prepared from nanodiamonds containing nitrogen-vacancy centers. The translucent, near-spherical shell architecture enables quick and highly effective decoration of particles with various (bio)molecules using click chemistry. The particles show superior behavior in cell experiments and they fully exploit the unique photophysical properties of nitrogen-vacancy centers.
Fluorescent Nanodiamonds I. Rehor, J. Slegerova, J. Kucka, V. Proks, V. Petrakova, M.-P. Adam, F. Treussart, S. Turner, S. Bals, P. Sacha, M. Ledvina, A. M. Wen, N. F. Steinmetz, P. Cigler* _________________ 1106–1115 Fluorescent Nanodiamonds Embedded in Biocompatible Translucent Shells
1034 www.small-journal.com
© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
small 2014, 10, No. 6, 1032–1037
The gadolinium chelate coated gold nanoparticles (Au@DTDTPA-Gd50) which were designed as contrast agents for magnetic resonance imaging (MRI) also behave as radiosensitizers. Their followup by MRI allows determining the delay between the irradiation of the tumor and the injection of the nanoparticles. As a result, the use of Au@DTDTPA-Gd50 nanoparticles leads to the improvement of the effect of radiotherapy.
Contrast Agents
Doped small-molecule organic nanoparticles (NPs) are used in a new strategy to achieve excellent fluorescent probes with high brightness, large Stokes shifts and tunable emissions for in vitro and in vivo imaging. The results indicate that doped NPs obtained by this strategy are promising as a fluorescent probe in biomedical applications.
Fluorescent Nanoparticles
I. Miladi, C. Alric, S. Dufort, P. Mowat, A. Dutour, C. Mandon, G. Laurent, E. Bräuer-Krisch, N. Herath, J.-L. Coll, M. Dutreix, F. Lux, R. Bazzi, C. Billotey, M. Janier, P. Perriat, G. L. Duc,* S. Roux,* O. Tillement ______________ 1116–1124 The In Vivo Radiosensitizing Effect of Gold Nanoparticles Based MRI Contrast Agents
J. Yu, X. J. Diao, X. J. Zhang,* X. F. Chen, X. J. Hao, W. Li, X. H. Zhang,* C.-S. Lee* ________________ 1125–1132 Water-Dispersible, pH-Stable and Highly-Luminescent Organic Dye Nanoparticles with Amplified Emissions for In Vitro and In Vivo Bioimaging
A smart nanovehicle for use as a novel drug nanocarrier is designed based on a supramolecular peptide-amphiphile system (SPAS). SPAS exists as a welldefined nanostructure at pH 7.4, but the whole SPAS system disassembles at pH 6.2. Because SPAS can encapsulate anticancer drugs at normal physiological conditions, and it can disassemble to release the drug at the pH levels found inside tumor cells.
Intracellular Drug Delivery
The future achievement of depth tissue real in vivo imaging requires the development of novel efficient infrared fluorescence nanoparticles. In this work, the potential application of Nd3+-doped LaF3 nanoparticles is reported for fluorescence bioimaging based on their three main emission channels of Nd3+ ions (first and second biological windows). High contrast and low toxicity are obtained, both in vivo and in vitro, using 1.06 μm.
Bioimaging
small 2014, 10, No. 6, 1032–1037
X. Xu, Y. Li, H. Li, R. Liu, M. Sheng, B. He, Z. Gu* ______________ 1133–1140 Smart Nanovehicles Based on pH-Triggered Disassembly of Supramolecular Peptide-Amphiphiles for Efficient Intracellular Drug Delivery
U. Rocha, K. U. Kumar, C. Jacinto, I. Villa, F. Sanz-Rodríguez, M. del Carmen Iglesias de la Cruz, A. Juarranz, E. Carrasco, F. C. J. M. van Veggel, E. Bovero, J. G. Solé, D. Jaque* _________1141–1154 Neodymium-Doped LaF3 Nanoparticles for Fluorescence Bioimaging in the Second Biological Window
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contents Osmocapsules are synthesized to provide tools for the direct measurement of osmotic pressure. Double-emulsion drops with an ultra-thin shell serve as templates to prepare microcapsules containing standard osmotic strength. The osmocapsules, subjected to positive osmotic pressure, exhibit discernible buckling, thereby enabling the measurement of the pressure. Moreover, these injectable osmocapsules are potentially useful for in-vivo pressure measurements and triggered release of drugs.
Microcapsules S.-H. Kim,* T. Y. Lee, S. S. Lee _________________ 1155–1162 Osmocapsules for Direct Measurement of Osmotic Strength
Quantum Dots
The coating dynamics of nanocrystal micelles is studied by monitoring in situ the energy transfer from quantum dot core to dye-labeled lipids. The dependences of lipid exchange on concentration, temperature and solvent are investigated. Exchange rate constant and activation energy are determined by fitting the results.
Y. Zhao, P. Schapotschnikow, T. Skajaa, T. J. H. Vlugt, W. J. M. Mulder, C. de Mello Donegá, A. Meijerink* _____________ 1163–1170 Probing Lipid Coating Dynamics of Quantum Dot Core Micelles via Förster Resonance Energy Transfer
MgO Nanoparticles Y. H. Leung, A. M. C. Ng, X. Xu, Z. Shen, L. A. Gethings, M. T. Wong, C. M. N. Chan, M. Y. Guo, Y. H. Ng, A. B. Djurišic´,* P. K. H. Lee,* W. K. Chan, L. H. Yu, D. L. Phillips, A. P. Y. Ma, F. C. C. Leung _____________ 1171–1183
Robust antibacterial activity on Escherichia coli cells in the absence of ROS production is demonstrated. Multiple lines of evidence clearly show the absence of oxidative stress and indicate that the primary mechanism of cell death is related to cell membrane damage, which does not appear to be due to lipid peroxidation.
Mechanisms of Antibacterial Activity of MgO: Non-ROS Mediated Toxicity of MgO Nanoparticles Towards Escherichia coli
Self-Assembly E. Huynh, J. F. Lovell, R. Fobel, G. Zheng* ________________1184–1193
Micrometer-sized vesicles generated from a porphyrin-lipid bilayer demonstrate the ability to induce membrane permeability, forming a large pore which then self-seals upon laser irradiation. The precise control associated with this technique allows a variety of microreactor applications such as DNA hybridization and enzyme reactions.
Optically Controlled Pore Formation in Self-Sealing Giant Porphyrin Vesicles
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The influence of ligand anchor and bridging groups on the optical and electronic properties of pyrite nanocrystal thin films is investigated systematically. The thin film absorption onset shifts up to 100 meV to the red and the differential conductance varies over four orders of magnitude for the different ligands with ammonium sulfides and thiolated aromatic linkers showing the largest effects.
Semiconductor Nanocrystals
Magnetic (bMR) nanosensors are used to screen a library of small molecules for binding to and inhibition of the Anthrax lethal factor (LF). Out of 30 different bMR nanosensors, only two, containing sulindac and fusaric acid on their surfaces, were able to inhibit the protease activity of LF. Meanwhile, the sulindac bMR nanosensor by itself was a potent inhibitor of LF macrophage cytoxocity with an IC50 in the low nanomolar range.
Magnetic Nanosensors
Single-chain conjugated polymer (CP) dots embedded nanoparticles (NPs) are fabricated via encapsulation method by optimization of CP and matrix feed concentrations. DSPE-PEG-Maleimide as the polymer matrix endows NPs with surface maleimide groups, which favours easy conjugation with TAT peptide via click chemistry to pres erve its biofunctions. The obtained CPNPs show high brightness and good biocompatibility, which allow cell tracing for over 9 generations, superior to commercial cell tracker Qtracker 585.
Conjugated Polymers
W. Li, T. Dittrich,* F. Jäckel,* J. Feldmann* ______________1194–1201 Optical and Electronic Properties of Pyrite Nanocrystal Thin Films: the Role of Ligands
O. J. Santiesteban, C. Kaittanis, J. M. Perez* _______________1202–1211 Identification of Toxin Inhibitors Using a Magnetic Nanosensor-Based Assay
G. Feng, K. Li, J. Liu, D. Ding, B. Liu* ___________________ 1212–1219 Bright Single-Chain Conjugated Polymer Dots Embedded Nanoparticles for Long-Term Cell Tracing and Imaging
Nanoshell on nanocapsule: Surface seeding method constructs gold nanoshell on liquid perfluorocarbon nanocapsules, giving the echogenic contrast agent extra functionalities of CT contrast enhancement and photo-induced hyperthermia therapy. The nanocapsule theranostic agent is demonstrated to utilize combined dual modal ultrasound/CT contrast imaging and photothermal tumor ablation, which may have potential impact on methodology of cancer diagnosis and therapy.
Nanomedicine H. Ke, X. Yue, J. Wang, S. Xing, Q. Zhang, Z. Dai,* J. Tian,* S. Wang, Y. Jin ____________ 1220–1227 Gold Nanoshelled Liquid Perfluorocarbon Nanocapsules for Combined Dual Modal Ultrasound/CT Imaging and Photothermal Therapy of Cancer
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