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1.
Nanomaterials (Basel) ; 11(2)2021 Feb 09.
Artigo em Inglês | MEDLINE | ID: mdl-33572253

RESUMO

Square-shaped or rectangular nanoparticles (NPs) of lanthanum oxide (LaOx) were synthesized and layered by convective self-assembly to demonstrate an analog memristive device in this study. Along with non-volatile analog memory effect, selection diode property could be co-existent without any implementation of heterogeneous multiple stacks with ~1 µm thick LaOx NPs layer. Current-voltage (I-V) behavior of the LaOx NPs resistive switching (RS) device has shown an evolved current level with memristive behavior and additional rectification functionality with threshold voltage. The concurrent memristor and diode type selector characteristics were examined with electrical stimuli or spikes for the duration of 10-50 ms pulse biases. The pulsed spike increased current levels at a read voltage of +0.2 V sequentially along with ±7 V biases, which have emulated neuromorphic operation of long-term potentiation (LTP). This study can open a new application of rare-earth LaOx NPs as a component of neuromorphic synaptic device.

2.
Materials (Basel) ; 13(19)2020 Oct 02.
Artigo em Inglês | MEDLINE | ID: mdl-33023165

RESUMO

Magnetic hydrogels have been commonly used in biomedical applications. As magnetite nanoparticles (MNPs) exhibit peroxidase enzyme-like activity, magnetic hydrogels have been actively used as signal transducers for biomedical assays. Droplet microfluidics, which uses photoinitiated polymerization, is a preferred method for the synthesis of magnetic hydrogels. However, light absorption by MNPs makes it difficult to obtain fully polymerized and homogeneous magnetic hydrogels through photoinitiated polymerization. Several methods have been reported to address this issue, but few studies have focused on investigating the light absorption properties of photoinitiators. In this study, we developed a simple method for the synthesis of poly(ethylene glycol) (PEG)-based uniform magnetic hydrogels that exploits the high ultraviolet absorption of a photoinitiator. Additionally, we investigated this effect on shape deformation and structural uniformity of the synthesized magnetic hydrogels. Two different photoinitiators, Darocur 1173 and lithium phenyl (2,4,6-trimethylbenzoyl) phosphinate (LAP), with significantly different UV absorption properties were evaluated based on the synthesis of magnetic hydrogels. The magnetic characteristics of the PEG-stabilized MNPs in hydrogels were investigated with a vibrating sample magnetometer. Finally, the colorimetric detection of hydrogen peroxide and glucose was conducted based on the enzyme-like property of MNPs and repeated several times to observe the catalytic activity of the magnetic hydrogels.

3.
ACS Appl Mater Interfaces ; 12(45): 51092-51101, 2020 Nov 11.
Artigo em Inglês | MEDLINE | ID: mdl-33108175

RESUMO

Phase change materials (PCMs) have received considerable attention for various latent heat storage systems for efficient thermal energy utilization. Herein, a facile and fast method for the bulk nanoencapsulation of organic PCMs is proposed, based on the thermodynamically spontaneous spreading phenomenon of three immiscible liquid phases. In this approach, a complete engulfing of PCM nanodroplets (core phase) by immiscible prepolymer droplets (coating phase), both of which are bulk-dispersed in another immiscible medium (continuous phase), is thermodynamically driven by the relation between the surface energies of the core, coating, and continuous phases. To demonstrate the proposed method, melted n-docosane (PCM, core phase) nanodroplets are completely engulfed within a couple of minutes by immiscible polyethylene glycol diacrylate (PEGDA, coating phase) in an aqueous poly(vinyl alcohol) solution (continuous phase), and the PEGDA layer quickly cross-linked upon UV irradiation to form a rigid shell protecting the PCM core. As-produced PCM nanocapsules display promising heat storage and release performances as well as high durability in repeated heating-cooling cycles in both dry and wet states. The proposed process may serve as a useful platform for bulk production of PCM nanocapsules with various core and shell compositions in a facile, fast, and scalable way.

4.
Langmuir ; 36(32): 9424-9435, 2020 Aug 18.
Artigo em Inglês | MEDLINE | ID: mdl-32659098

RESUMO

Capillary suspensions are ternary solid-liquid-liquid systems produced via the addition of a small amount of secondary fluid to the bulk fluid that contained the dispersed solid particles. The secondary fluid could exert strong capillary forces between the particles and dramatically change the rheological properties of the suspension. So far, research has focused on capillary suspensions that consist of additive-free fluids, whereas capillary suspensions with additives, particularly those of large molecular weight that are highly relevant for industrial purposes, have been relatively less studied. In this study, we performed a systematic analysis of the properties of capillary suspensions that consist of paraffin oil (bulk phase), water (secondary phase), and α-Al2O3 microparticles (particle phase), in which the aqueous secondary phase contained an important eco-friendly polymeric binder, sodium alginate (SA). It was determined that the yield stress of the suspension increased significantly with the increase in the SA content in the aqueous secondary phase, which was attributed to the synergistic effect of the capillary force and hydrogen bonding force that may be related to the increase in the number of capillary bridges. The amounts of SA used to induce a significant change in the yield stress in this study were very small (<0.02% of the total sample volume). The addition of Ca2+ ions to the SA-containing secondary phase further increased the yield stress with possible gelation of the SA chains-in the presence of excess Ca2+ ions, however, the yield stress decreased because of the microscopic phase separation that occurred in the aqueous secondary phase. The microstructures of the sintered porous materials that were produced by using capillary suspensions as precursors were qualitatively well correlated to the rheological behavior of the precursor suspensions, suggesting a new method for the subtle control of the microstructures of porous materials using the addition of minute amounts of polymeric additives.

5.
RSC Adv ; 9(27): 15257-15264, 2019 May 14.
Artigo em Inglês | MEDLINE | ID: mdl-35514812

RESUMO

Phosphate is a ubiquitous pollutant in aquatic systems, and increasingly stringent post-treatment phosphate effluent standards necessitate increasingly efficient removal techniques. In this study, mesoporous lanthanum hydroxide (MLHO) was synthesized by a hard-template method using ordered mesoporous silica, and its potential as an adsorbent for high-efficiency phosphate removal in aqueous solutions was tested. The porosity characteristics of MLHOs were controlled by adjusting the template structure and synthesis conditions. MLHO adsorbents showed great potential for phosphate removal from solutions containing both high and low initial phosphate concentrations. The phosphate adsorption capacity of MLHO strongly depended on its surface area as this process was governed by monolayer adsorption. Moreover, the phosphate removal performance of MLHO was affected by its structural properties. MLHO showed a high adsorption capacity of 109.41 mg P g-1 at 28 °C (q m by the Langmuir isotherm model). Further, it showed ultrafast adsorption in a solution with low initial concentration of 2 mg P/L; within the first 10 min, 99.8% of phosphate was removed, and the phosphorus concentration remaining in the solution dramatically reduced to 4 µg P/L. These findings suggest that MLHO adsorbent is a good candidate for rapid and efficient low-concentration phosphate removal to meet the increasingly stringent discharge standards for wastewater treatment plants.

6.
J Nanosci Nanotechnol ; 15(6): 4126-35, 2015 Jun.
Artigo em Inglês | MEDLINE | ID: mdl-26369021

RESUMO

The objective of this study was to assess cytotoxicity of engineered MnO nanoparticles by quantifying the reactive oxygen species (ROS) related genes (glutathione S-transferase (GST) and catalase) using real time-polymerase chain reaction (RT-PCR) and molecular beacon (MB) technologies. Monodisperse MnO nanoparticles of 14 nm in size were synthesized by the encapsulation of polyethyleneglycol (PEG)-phospholipid shell around the MnO core to endow high water-dispersibility and biocompatibility. In vitro cytotoxicity was evaluated at different concentrations (10, 50 and 100 µg/ml) and incubation times (12, 24 and 48 h) with human cancer cell lines (glioblastoma, lung adenocarcinoma and neuroblastoma cells). Both genetic and cellular cytotoxic screening methods produced consistent results, showing that GST and catalase ROS gene expression was maximized in 24 h incubation at 100 µg/ml concentration of MnO nanoparticles for each cell line. However, the cytotoxicity effect of the PEG-phospholipid coated MnO nanoparticle was not significant compared with control experiments, demonstrating its high potential in the applications of nanomedicines for a diagnostic and therapeutic tool.


Assuntos
Catalase/metabolismo , Glutationa Transferase/metabolismo , Compostos de Manganês/química , Nanopartículas/química , Estresse Oxidativo/genética , Óxidos/química , Catalase/análise , Catalase/genética , Linhagem Celular Tumoral , Expressão Gênica , Glutationa Transferase/análise , Glutationa Transferase/genética , Humanos , Imagem Molecular , Reação em Cadeia da Polimerase em Tempo Real
7.
J Nanosci Nanotechnol ; 15(4): 2702-14, 2015 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-26353484

RESUMO

We report the synthesis of monodisperse calcium carbonate (CaCO3) (nano)particles having either a cubic or spherical structure by reacting calcium nitrate with either sodium carbonate or citric acid, respectively, in the presence of cetyltrimethylammonium bromide (CTAB) via the sonication method. For comparison, CaCO3 (nano)particles were synthesized by the same method in the absence of CTAB and also via the standard hydrothermal method using CTAB. The synthesized CaCO3 (nano)particles were analyzed by various physico-chemical characterization techniques such as X-ray diffraction (XRD), Fourier transform infra-red spectroscopy, thermogravimetric analysis, and scanning electron microscopy with energy-dispersive spectrometer. It was found that the CaCO3 (nano)particles were highly pure with high crystallinity and exhibited the calcite polymorph phase as revealed by the XRD analysis. In addition, the analytical results showed that the (nano)particles prepared in the presence of CTAB by the sonication method had high structural ordering and no agglomeration as compared to the (nano)particles prepared by the hydrothermal method. Therefore, our sonication method is a new way to prepare shape-controlled CaCO3 (nano)particles under mild reaction conditions.


Assuntos
Carbonato de Cálcio/química , Compostos de Cetrimônio/química , Nanopartículas/química , Sonicação/métodos , Cetrimônio , Nanotecnologia
8.
J Colloid Interface Sci ; 439: 134-8, 2015 Feb 01.
Artigo em Inglês | MEDLINE | ID: mdl-25463185

RESUMO

Hollow MnOxPy and Pt/MnOxPy yolk/shell nanoparticles were fabricated via the nanoscale acid-etching process from the solid MnO and Pt/MnO core/shell nanoparticles, respectively. In the synthesis, alkylphosphonic acid impurity in trioctylphosphine oxide was a key component, resulting in amorphous hollow metal phosphate nanoparticles. Hollow nanoparticles containing Mn(2+) ions showed positively enhanced T1 relaxation, in which the r1 values of the hollow MnOxPy and Pt/MnOxPy yolk/shell were greater than that of the original MnO nanocrystals. The increased surface area of the hollow nanoparticles enhanced interaction between Mn(2+) ions of the nanoparticle surface and water molecules. Cytotoxicity experiment revealed that Mn ions released from hollow walls of the MnOxPy nanoparticles were responsible for the cytotoxicity, while Pt ions from the Pt/MnOxPy yolk/shell were not released in the cells. These nanoparticles provide potential insights into an anticancer drug, enabling simultaneous T1 magnetic resonance imaging (MRI) and therapy.


Assuntos
Meios de Contraste/química , Imageamento por Ressonância Magnética , Manganês/química , Nanoestruturas/química , Ácido Oleico/química , Células Cultivadas , Humanos , Nanopartículas Metálicas/química , Propriedades de Superfície
9.
Langmuir ; 30(21): 6197-208, 2014 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-24805794

RESUMO

We have designed a set of multifunctional and multicoordinating polymer ligands that are optimally suited for surface functionalizing iron oxide and potentially other magnetic nanoparticles (NPs) and promoting their integration into biological systems. The amphiphilic polymers are prepared by coupling (via nucleophilic addition) several amine-terminated dopamine anchoring groups, poly(ethylene glycol) moieties, and reactive groups onto a poly(isobutylene-alt-maleic anhydride) (PIMA) chain. This design greatly benefits from the highly efficient and reagent-free one-step reaction of maleic anhydride groups with amine-containing molecules. The availability of several dopamine groups in the same ligand greatly enhances the ligand affinity, via multiple coordination, to the magnetic NPs, while the hydrophilic and reactive groups promote colloidal stability in buffer media and allow subsequent conjugation with target biomolecules. Iron oxide nanoparticles ligand exchanged with these polymer ligands have a compact hydrodynamic size and exhibit enhanced long-term colloidal stability over the pH range of 4-12 and in the presence of excess electrolytes. Nanoparticles ligated with terminally reactive polymers have been easily coupled to target dyes and tested in live cell imaging with no measurable cytotoxicity. Finally, the resulting hydrophilic nanoparticles exhibit large and size-dependent r2 relaxivity values.


Assuntos
Coloides/química , Compostos Férricos/química , Magnetismo , Nanopartículas Metálicas/química , Polímeros/química , Amidas/química , Aminas/química , Sobrevivência Celular , Meios de Contraste/química , Eletrólitos , Células HeLa , Humanos , Hidrodinâmica , Concentração de Íons de Hidrogênio , Ligantes , Luz , Imageamento por Ressonância Magnética , Anidridos Maleicos/química , Microscopia de Fluorescência , Nanopartículas/química , Iodeto de Potássio/química , Espalhamento de Radiação
10.
Artigo em Inglês | MEDLINE | ID: mdl-24123961

RESUMO

Magnetic resonance imaging (MRI) is one of the most powerful molecular imaging techniques and can noninvasively visualize and quantify biological processes within the living organisms. The introduction of exogenous contrast agents has allowed specific visualization of biological targets as well as enhanced the sensitivity of MRI. Recently, paramagnetic inorganic nanoparticles showing positive T(1) contrast effect have been investigated as T(1) MRI contrast agents. Since the first trials of spherical nanoparticles of manganese oxide and gadolinium oxide, inorganic nanoparticles of various compositions and shapes have been used for in vivo and in vitro MRI because of their distinct signal enhancement in MR images. However, for clinical applications, important and complex issues such as safety and efficiency should be investigated by active research encompassing multiple disciplines, including chemistry, biology, biomedical engineering, and medicine.


Assuntos
Meios de Contraste , Imageamento por Ressonância Magnética , Nanopartículas de Magnetita , Animais , Gadolínio , Humanos , Ferro , Manganês , Camundongos
11.
Nat Mater ; 12(4): 359-66, 2013 Apr.
Artigo em Inglês | MEDLINE | ID: mdl-23416726

RESUMO

Three-photon excitation is a process that occurs when three photons are simultaneously absorbed within a luminophore for photo-excitation through virtual states. Although the imaging application of this process was proposed decades ago, three-photon biomedical imaging has not been realized yet owing to its intrinsic low quantum efficiency. We herein report on high-resolution in vitro and in vivo imaging by combining three-photon excitation of ZnS nanocrystals and visible emission from Mn(2+) dopants. The large three-photon cross-section of the nanocrystals enabled targeted cellular imaging under high spatial resolution, approaching the theoretical limit of three-photon excitation. Owing to the enhanced Stokes shift achieved through nanocrystal doping, the three-photon process was successfully applied to high-resolution in vivo tumour-targeted imaging. Furthermore, the biocompatibility of ZnS nanocrystals offers great potential for clinical applications of three-photon imaging.


Assuntos
Nanopartículas/química , Sulfetos/química , Compostos de Zinco/química , Humanos , Manganês/química , Imagens de Fantasmas , Fótons , Células Tumorais Cultivadas
12.
Nano Lett ; 12(8): 4018-24, 2012 Aug 08.
Artigo em Inglês | MEDLINE | ID: mdl-22784189

RESUMO

Electrospun polymer nanofibers with entrapped magnetic nanoparticles (magnetic NP-NF) represent a novel scaffold substrate that can be functionalized for single-step isolation and activation of specific lymphocyte subsets. Using a surface-embedded T cell receptor ligand/trigger (anti-CD3 monoclonal antibody), we demonstrate, as proof of principle, the use of magnetic NP-NF to specifically isolate, enrich, and activate CD3(+) T cells from a heterogeneous cell mixture, leading to preferential expansion of CD8(+)CD3(+) T cells. The large surface area, adjustable antibody density, and embedded paramagnetic properties of the NP-NF permitted enhanced activation and expansion; its use represents a strategy that is amenable to an efficient selection process for adoptive cellular therapy as well as for the isolation of other cellular subsets for downstream translational applications.


Assuntos
Álcoois , Complexo CD3/metabolismo , Separação Celular/métodos , Ativação Linfocitária , Nanopartículas de Magnetita/química , Nanofibras/química , Linfócitos T/citologia , Linfócitos T/metabolismo , Animais , Anticorpos Monoclonais/imunologia , Anticorpos Monoclonais/metabolismo , Complexo CD3/imunologia , Camundongos , Camundongos Endogâmicos C57BL , Linfócitos T/imunologia
13.
J Am Chem Soc ; 134(13): 6006-17, 2012 Apr 04.
Artigo em Inglês | MEDLINE | ID: mdl-22394283

RESUMO

We investigated the charge transfer interactions between luminescent quantum dots (QDs) and redox active dopamine. For this, we used pH-insensitive ZnS-overcoated CdSe QDs rendered water-compatible using poly (ethylene glycol)-appended dihydrolipoic acid (DHLA-PEG), where a fraction of the ligands was amine-terminated to allow for controlled coupling of dopamine-isothiocyanate onto the nanocrystal. Using this sample configuration, we probed the effects of changing the density of dopamine and the buffer pH on the fluorescence properties of these conjugates. Using steady-state and time-resolved fluorescence, we measured a pronounced pH-dependent photoluminescence (PL) quenching for all QD-dopamine assemblies. Several parameters affect the PL loss. First, the quenching efficiency strongly depends on the number of dopamines per QD-conjugate. Second, the quenching efficiency is substantially increased in alkaline buffers. Third, this pH-dependent PL loss can be completely eliminated when oxygen-depleted buffers are used, indicating that oxygen plays a crucial role in the redox activity of dopamine. We attribute these findings to charge transfer interactions between QDs and mainly two forms of dopamine: the reduced catechol and oxidized quinone. As the pH of the dispersions is changed from acidic to basic, oxygen-catalyzed transformation progressively reduces the dopamine potential for oxidation and shifts the equilibrium toward increased concentration of quinones. Thus, in a conjugate, a QD can simultaneously interact with quinones (electron acceptors) and catechols (electron donors), producing pH-dependent PL quenching combined with shortening of the exciton lifetime. This also alters the recombination kinetics of the electron and hole of photoexcited QDs. Transient absorption measurements that probed intraband transitions supported those findings where a simultaneous pronounced change in the electron and hole relaxation rates was measured when the pH was changed from acidic to alkaline.


Assuntos
Dopamina/química , Medições Luminescentes , Pontos Quânticos , Eletroquímica , Concentração de Íons de Hidrogênio , Fenômenos Ópticos , Oxirredução , Oxigênio/química , Polietilenoglicóis/química , Ácido Tióctico/análogos & derivados , Ácido Tióctico/química
14.
Adv Drug Deliv Rev ; 64(2): 138-66, 2012 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-21982955

RESUMO

In this report we review some of the recent progress made for enhancing the biocompatibility of luminescent quantum dots (QDs) and for developing targeted bio-inspired applications centered on live cell imaging and sensing. We start with a detailed analysis of the surface functionalization strategies developed thus far, and discuss their effectiveness for providing long term stability of the quantum dots in biological media, to changes in pH and to added electrolytes. We then discuss the available conjugation techniques to couple QDs to a variety of biological receptors and compare their effectiveness. In particular, we highlight the implementation of new strategies such as the use of copper-free cyclo-addition reaction (CLICK) chemistry and chemo-selective ligation. We then discuss the advances made for intracellular delivery where ideas such as receptor-driven endocytosis and uptake promoted by cell penetrating peptides are used. We then describe a few representative examples where QDs have been used to investigate specific cell biology processes. Such processes include binding of QDs conjugated to the nerve growth factor to membrane specific receptors and intracellular uptake, tracking of membrane protein at the single molecule level, and recognition of ligand bound QDs by T cell receptors. We conclude by discussing issues of toxicity associated with the use of QDs in biology.


Assuntos
Pontos Quânticos , Animais , Técnicas Biossensoriais , Diagnóstico por Imagem , Sistemas de Liberação de Medicamentos , Humanos , Luminescência , Semicondutores
15.
ACS Nano ; 6(1): 389-99, 2012 Jan 24.
Artigo em Inglês | MEDLINE | ID: mdl-22176202

RESUMO

We have designed, prepared, and tested a new set of multidentate catechol- and polyethylene glycol (PEG)-derivatized oligomers, OligoPEG-Dopa, as ligands that exhibit strong affinity to iron oxide nanocrystals. The ligands consist of a short poly(acrylic acid) backbone laterally appended with several catechol anchoring groups and several terminally functionalized PEG moieties to promote affinity to aqueous media and to allow further coupling to target molecules (bio and others). These multicoordinating PEGylated oligomers were prepared using a relatively simple chemical strategy based on N,N'-dicyclohexylcarbodiimide (DCC) and N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide (EDC) condensation. The ability of these catechol-functionalized oligomers to impart long-term colloidal stability to the nanoparticles is compared to other control ligands, namely, oligomers presenting several carboxyl groups and monodentate ligands presenting either one catechol or one carboxyl group. We found that the OligoPEG-Dopa ligands provide rapid ligand exchange, and the resulting nanoparticles exhibit greatly enhanced colloidal stability over a broad pH range and in the presence of excess electrolytes; stability is notably improved compared to non-catechol presenting molecular or oligomer ligands. By inserting controllable fractions of azide-terminated PEG moieties, the nanoparticles (NPs) become reactive to complementary functionalities via azide-alkyne cycloaddition (Click), which opens up the possibility of biological targeting of such stable NPs. In particular, we tested the Click coupling of azide-functionalized nanoparticles to an alkyne-modified dye. We also measured the MRI T(2) contrast of the OligoPEG-capped Fe(3)O(4) nanoparticles and applied MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide) assay to test the potential cytotoxicity of these NPs to live cells; we found no measurable toxicity to live cells.


Assuntos
Catecóis/química , Ácido Láctico/química , Nanopartículas de Magnetita/química , Nanopartículas de Magnetita/toxicidade , Microglia/citologia , Microglia/efeitos dos fármacos , Ácido Poliglicólico/química , Animais , Linhagem Celular , Sobrevivência Celular/efeitos dos fármacos , Copolímero de Ácido Poliláctico e Ácido Poliglicólico , Ratos
16.
Langmuir ; 28(5): 2761-72, 2012 Feb 07.
Artigo em Inglês | MEDLINE | ID: mdl-22201293

RESUMO

We have developed a new set of multifunctional multidentate OligoPEG ligands, each containing a central oligomer on which were laterally grafted several short poly(ethylene glycol) (PEG) moieties appended with either thioctic acid (TA) or terminally reactive groups. Reduction of the TAs (e.g., in the presence of NaBH(4)) provides dihydrolipoic acid (DHLA)-appended oligomers. Here the insertion of PEG segments in the ligand structure promotes water solubility and reduces nonspecific interactions, while TA and DHLA groups provide multidentate anchoring onto Au nanoparticles (AuNPs) and ZnS-overcoated semiconductor quantum dots (QDs), respectively. The synthetic route involves simple coupling chemistry using N,N-dicylohexylcarbodiimide (DCC). Water-soluble QDs and AuNPs capped with these ligands were prepared via cap exchange. As prepared, the nanocrystals dispersions were aggregation-free, homogeneous, and stable for extended periods of time over pH ranging from 2 to 14 and in the presence of excess electrolyte (2 M NaCl). The new OligoPEG ligands also allow easy integration of tunable functional and reactive groups within their structures (e.g., azide or amine), which imparts surface functionalities to the nanocrystals and opens up the possibility of bioconjugation with specific biological molecules. The improved colloidal stability combined with reactivity offer the possibility of using the nanocrystals as biological probes in an array of complex and biologically relevant media.


Assuntos
Materiais Biocompatíveis/química , Ouro/química , Nanopartículas Metálicas/química , Polietilenoglicóis/química , Sulfetos/química , Compostos de Zinco/química , Materiais Biocompatíveis/síntese química , Ligantes , Pontos Quânticos , Semicondutores , Solubilidade , Ácido Tióctico/análogos & derivados , Ácido Tióctico/química
17.
J Am Chem Soc ; 133(32): 12624-31, 2011 Aug 17.
Artigo em Inglês | MEDLINE | ID: mdl-21744804

RESUMO

Uniform and extremely small-sized iron oxide nanoparticles (ESIONs) of < 4 nm were synthesized via the thermal decomposition of iron-oleate complex in the presence of oleyl alcohol. Oleyl alcohol lowered the reaction temperature by reducing iron-oleate complex, resulting in the production of small-sized nanoparticles. XRD pattern of 3 nm-sized nanoparticles revealed maghemite crystal structure. These nanoparticles exhibited very low magnetization derived from the spin-canting effect. The hydrophobic nanoparticles can be easily transformed to water-dispersible and biocompatible nanoparticles by capping with the poly(ethylene glycol)-derivatized phosphine oxide (PO-PEG) ligands. Toxic response was not observed with Fe concentration up to 100 µg/mL in MTT cell proliferation assay of POPEG-capped 3 nm-sized iron oxide nanoparticles. The 3 nm-sized nanoparticles exhibited a high r(1) relaxivity of 4.78 mM(-1) s(-1) and low r(2)/r(1) ratio of 6.12, demonstrating that ESIONs can be efficient T(1) contrast agents. The high r(1) relaxivities of ESIONs can be attributed to the large number of surface Fe(3+) ions with 5 unpaired valence electrons. In the in vivo T(1)-weighted magnetic resonance imaging (MRI), ESIONs showed longer circulation time than the clinically used gadolinium complex-based contrast agent, enabling high-resolution imaging. High-resolution blood pool MR imaging using ESIONs enabled clear observation of various blood vessels with sizes down to 0.2 mm. These results demonstrate the potential of ESIONs as T(1) MRI contrast agents in clinical settings.


Assuntos
Meios de Contraste/síntese química , Compostos Férricos/síntese química , Imageamento por Ressonância Magnética/métodos , Nanopartículas/química , Animais , Linhagem Celular Tumoral , Meios de Contraste/química , Feminino , Compostos Férricos/química , Humanos , Angiografia por Ressonância Magnética/métodos , Nanopartículas/ultraestrutura , Tamanho da Partícula , Fosfinas/síntese química , Fosfinas/química , Polietilenoglicóis/síntese química , Polietilenoglicóis/química , Ratos
18.
Proteomics ; 11(2): 309-18, 2011 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-21204257

RESUMO

Trypsin-coated magnetic nanoparticles (EC-TR/NPs), prepared via a simple multilayer random crosslinking of the trypsin molecules onto magnetic nanoparticles, were highly stable and could be easily captured using a magnet after the digestion was complete. EC-TR/NPs showed a negligible loss of trypsin activity after multiple uses and continuous shaking, whereas the conventional immobilization of covalently attached trypsin on NPs resulted in a rapid inactivation under the same conditions due to the denaturation and autolysis of trypsin. A single model protein, a five-protein mixture, and a whole mouse brain proteome were digested at atmospheric pressure and 37°C for 12 h or in combination with pressure cycling technology at room temperature for 1 min. In all cases, EC-TR/NPs performed equally to or better than free trypsin in terms of both the identified peptide/protein number and the digestion reproducibility. In addition, the concomitant use of EC-TR/NPs and pressure cycling technology resulted in very rapid (∼1 min) and efficient digestions with more reproducible digestion results.


Assuntos
Enzimas Imobilizadas/metabolismo , Magnetismo , Nanopartículas/química , Proteínas/metabolismo , Proteômica/métodos , Tripsina/metabolismo , Animais , Encéfalo/metabolismo , Masculino , Camundongos , Camundongos Endogâmicos C57BL , Nanopartículas/ultraestrutura , Pressão , Proteoma/metabolismo , Proteômica/economia
19.
Biosens Bioelectron ; 26(7): 3192-9, 2011 Mar 15.
Artigo em Inglês | MEDLINE | ID: mdl-21242086

RESUMO

We demonstrate a highly sensitive electrochemical immunosensor based on the combined use of substrate recycling and carbon nanotubes (CNTs) coated with tyrosinase (TYR) and magnetic nanoparticles (MNP). Both TYR and MNP were immobilized on the surface of CNTs by covalent attachment, followed by additional cross-linking via glutaraldehyde treatment to construct multi-layered cross-linked TYR-MNP aggregates (M-EC-CNT). Magnetically capturable, highly active and stable M-EC-CNT were further conjugated with primary antibody against a target analyte of hIgG, and used for a sandwich-type immunoassay with a secondary antibody conjugated with alkaline phosphatase (ALP). In the presence of a target analyte, a sensing assembly of M-EC-CNT and ALP-conjugated antibody was attracted onto a gold electrode using a magnet. On an electrode, ALP-catalyzed hydrolysis of phenyl phosphate generated phenol, and successive TYR-catalyzed oxidation of phenol produced electrochemically measurable o-quinone that was converted to catechol in a scheme of substrate recycling. Combination of highly active M-EC-CNT and substrate recycling for the detection of hIgG resulted in a sensitivity of 27.6 nA ng(-1) mL(-1) and a detection limit of 0.19 ng mL(-1) (1.2 pM), respectively, representing better performance than any other electrochemical immunosensors relying on the substrate recycling with the TYR-ALP combination. The present immunosensing system also displayed a long-term stability by showing a negligible loss of electrochemical detection signal even after reagents were stored in an aqueous buffer at 4°C for more than 6 months.


Assuntos
Técnicas Biossensoriais/métodos , Técnicas Eletroquímicas/métodos , Técnicas Imunoenzimáticas/métodos , Imunoglobulina G/análise , Monofenol Mono-Oxigenase/metabolismo , Nanopartículas/química , Agaricales/enzimologia , Enzimas Imobilizadas/química , Enzimas Imobilizadas/metabolismo , Humanos , Imunoglobulina G/imunologia , Magnetismo , Monofenol Mono-Oxigenase/química , Nanotubos de Carbono/química , Nanotubos de Carbono/ultraestrutura , Sensibilidade e Especificidade
20.
Bioprocess Biosyst Eng ; 33(1): 141-7, 2010 Jan.
Artigo em Inglês | MEDLINE | ID: mdl-19851786

RESUMO

Beta-glucosidase (betaG) can relieve the product inhibition of cellobiose in the cellulosic ethanol production by converting cellobiose into glucose. For the potential recycled uses, betaG was immobilized and stabilized in the form of enzyme coating on polymer nanofibers. The betaG coating (EC-betaG) was fabricated by crosslinking additional betaG molecules onto covalently attached betaG molecules (CA-betaG) via glutaraldehyde treatment. The initial activity of EC-betaG was 36 times higher than that of CA-betaG. After 20 days of incubation under shaking, CA-betaG and EC-betaG retained 33 and 91% of each initial activity, respectively. Magnetic nanofibers were also used for easy recovery and recycled uses of betaG coating. It is anticipated that the recycled uses of highly active and stable betaG coating can improve the economics of cellulosic ethanol production so long as economical materials are employed as a host of enzyme immobilization.


Assuntos
Celobiose/química , Enzimas Imobilizadas/química , Etanol , Glucose/química , Nanofibras/química , beta-Glucosidase/química
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