Biomolecule-nanoparticle hybrids for electrochemical biosensors

Inorganic nanoparticles (NPs) with attractive electronic, optical, magnetic, thermal and catalytic properties have attracted great interest due to their important applications in physics, chemistry, biology, medicine, materials science and interdisciplinary fields. Biomolecule-NP hybrid systems, which combine recognition and catalytic properties of biomolecules with electronic, optical, magnetic and catalytic properties of NPs, are particularly new materials with synergistic properties originating from the components of the hybrid composites. The biomolecule-NP hybrid system has excellent prospects for interfacing biological recognition events with electronic signal transduction so as to design a new generation of bioelectronic devices with high sensitivity.

Strain induced anomalous red shift in mesoscopic iron oxide prepared by a novel technique

Nano magnetic oxides are promising candidates for high density magnetic storage and other applications. Nonspherical mesoscopic iron oxide particles are also candidate materials for studying the shape, size and strain induced modifications of various physical properties viz. optical, magnetic and structural. Spherical and nonspherical iron oxides having an aspect ratio, ~2, are synthesized by employing starch and ethylene glycol and starch and water, respectively by a novel technique. Their optical, structural, thermal and magnetic properties are evaluated. A red shift of 0⋅24 eV is observed in the case of nonspherical particles when compared to spherical ones. The red shift is attributed to strain induced changes in internal pressure inside the elongated iron oxide particles. Pressure induced effects are due to the increased overlap of wave functions. Magnetic measurements reveal that particles are superparamagnetic. The marked increase in coercivity in the case of elongated particles is a clear evidence for shape induced anisotropy. The decreased specific saturation magnetization of the samples is explained on the basis of weight percentage of starch, a nonmagnetic component and is verified by TGA and FTIR studies. This technique can be modified for tailoring the aspect ratio and these particles are promising candidates for drug delivery and contrast enhancement agents in magnetic resonance imaging

Study on the observation of Eu(2+) and Eu(3+) valence states in low silica calcium aluminosilicate glasses

The optical, magnetic and structural properties of Eu doped low silica calcium aluminosilicate glasses were investigated. The optical absorption coefficient presented two bands at 39 246 and 29 416 cm(-1), which were assigned respectively to the 4f(7) ((8)S(7/2)) -> 4f(6) (4F(J)) 5d (T(2g)), and 4f(7) ((8)S(7/2)) -> 4f(6) (4F(J)) 5d (E(g)) transitions of Eu(2+). The fluorescence measured at 300 K on a sample doped with 0.5 wt% of Eu(2)O(3) exhibited a broad band centered at 17 350 cm(-1), which is attributed to the 4f(6)5d -> 4f(7) transition of Eu(2+), whereas the additional peaks are due to the (5)D(0) -> (7)F(J) (J = 1, 2, 4) transitions of Eu(3+). From magnetization and XANES data it was possible to evaluate the fractions of Eu(2+) and Eu(3+) for the sample doped with 0.5 and 5.0 wt% of Eu(2)O(3), the values of which were approximately 30 and 70%, respectively.

Nanopartículas magnéticas: o cobalto

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Curie temperatures and cell edges of ODP Leg 120 samples (Table 1)

Basalt samples recovered on Ocean Drilling Program Leg 120 from the Kerguelen Plateau were investigated by thermomagnetic analysis, X-ray diffraction, and ore microscopy. The basement samples could be divided into two groups based on Curie temperatures, cell-edge parameters, and optical magnetic mineralogy. Samples from Sites 748 and 750 underwent only low-temperature oxidation and displayed Curie temperatures for the titanomaghemites that ranged from 340° to 395°C. The basalts from Sites 747 and 749 mainly experienced high-temperature oxidation. High-temperature oxidation produced titanium-poor titanomagnetites with ilmenite-exsolution lamellae. Curie temperatures of the deuterically oxidized titanomaghemites varied from 490° to 620°C.

Multimodal polymer nanoparticles with combined 19F magnetic resonance and optical detection for tunable, targeted, multimodal imagingin vivo

Understanding the complex nature of diseased tissue in vivo requires development of more advanced nanomedicines, where synthesis of multifunctional polymers combines imaging multimodality with a biocompatible, tunable, and functional nanomaterial carrier. Here we describe the development of polymeric nanoparticles for multimodal imaging of disease states in vivo. The nanoparticle design utilizes the abundant functionality and tunable physicochemical properties of synthetically robust polymeric systems to facilitate targeted imaging of tumors in mice. For the first time, high-resolution 19F/1H magnetic resonance imaging is combined with sensitive and versatile fluorescence imaging in a polymeric material for in vivo detection of tumors. We highlight how control over the chemistry during synthesis allows manipulation of nanoparticle size and function and can lead to very high targeting efficiency to B16 melanoma cells, both in vitro and in vivo. Importantly, the combination of imaging modalities within a polymeric nanoparticle provides information on the tumor mass across various size scales in vivo, from millimeters down to tens of micrometers.

Optical and magnetic resonance studies of the interaction of metallo tetraphenylporphyrins with nitrobenzofuroxan

Metallo tetraphenylporphyrins form I : I molecular complexes with 4,6-dinitrobenzofuroxan. The molecular association is described in terms of T-n. interaction with porphyrins functioning as donors. The association constants and thermodynamic parameters have been evaluated using optical absorption and 'H nmr spectral methods. Based on the binding constants, the donor ability of various metalloporphyrins can be arranged in the following order: Pd(I1) > Co(I1) > Cu(I1) > Ni(I1) - VO(1V) - 2H > Zn(l1). Electron paramagnetic resonance studies of the complexes reveal that the IT-complexation results in changes in the electronic structure of the central metal ions which are reflected in the changes in the M-N 5 bonding. The dipolar contribution to the acceptor proton chemical shifts in the CoTPP complex has been partitioned from ring current contributions using the shifts observed in the ZnTPP complex. The shifts, along with the line broadening ratios observed for the CoTPP complex, are used to arrive at the possible solution structures of the complexes.

Magneto-transport and optical properties of diluted magnetic semiconductor Ga1-xMnxSb

We have studied magneto-transport and optical properties of Ga1-xMnxSb crystals (x = 0.01, 0.02, 0.03 and 0.04) grown by horizontal Bridgman method. Negative magnetoresistance and anomalous Hall effect have been observed below 10K. Temperature dependence of magnetization measurement shows a magnetic ordering below 10K which could arise from Ga1-xMnxSb alloy formation. Also, saturation in magnetization observed even at room temperature suggests the existence of ferromagnetic MnSb clusters. Reduction in band gap is observed with increasing Mn concentration in the crystals. Temperature dependence of band gap follows Bose-Einstein's model.

Optical properties of magnetic crystals

From symmetry considerations and using generalized Onsager relations, it is shown that 66 of the 90 magnetic classes, consisting of 29 single colour and 37 double colour ones, can exhibit what may be called the strain gyrotropic rotation. Similarly, 69 of the 90 magnetic classes, consisting of 21 single colour and 48 double colour ones, can exhibit what may be called the strain gyrotropic birefringence. A crystal in the class m3 or m3 m is interesting as it can exhibit strain gyrotropic rotation despite its being cubic and incapable of exhibiting gyrotropic rotation in the unstressed state. Similarly, a crystal in the class m3 m, is interesting as it can exhibit strain gyrotropic birefringence despite its being cubic and incapable of exhibiting gyrotropic birefringence in the unstressed state.

Influence of crossed electric and quantizing magnetic fields on the Einstein relation in nonlinear optical, optoelectronic and related materials: Simplified theory, relative comparison and suggestion for experimental determination

An attempt is made to study the Einstein relation for the diffusivity-to-mobility ratio (DMR) under crossed fields' configuration in nonlinear optical materials on the basis of a newly formulated electron dispersion law by incorporating the crystal field in the Hamiltonian and including the anisotropies of the effective electron mass and the spin-orbit splitting constants within the framework of kp formalisms. The corresponding results for III-V, ternary and quaternary compounds form a special case of our generalized analysis. The DMR has also been investigated for II-VI and stressed materials on the basis of various appropriate dispersion relations. We have considered n-CdGeAs2, n-Hg1-xCdxTe, n-In1-xGaxAsyP1-y lattice matched to InP, p-CdS and stressed n-InSb materials as examples. The DMR also increases with increasing electric field and the natures of oscillations are totally band structure dependent with different numerical values. It has been observed that the DMR exhibits oscillatory dependences with inverse quantizing magnetic field and carrier degeneracy due to the Subhnikov-de Haas effect. An experimental method of determining the DMR for degenerate materials in the present case has been suggested. (C) 2010 Elsevier B.V. All rights reserved.

Optical and magnetic properties of the exact PPP states of biphenyl

The low-lying singlets and triplets of biphenyl are obtained exactly within the PPP model using the diagrammatic valence bond method. The energy gaps within the singlet manifold as well as the lowest singlet-triplet gap are found to be in good agreement with experimental results. The two weak absorptions between 4·1 and 4·2 eV reported experimentally are attributed to the two states lying below the optical gap that become weakly allowed on breaking electron-hole and inversion symmetries. The observed blue shift of the spectral lines, attributed to a change in dihedral angle, on going from crystalline to solution to vapour phase is also well reproduced within the PPP model. The bond orders show that the ground singlet state is benzenoidal while the dipole excited state as well as the lowest triplet state are quinonoidal and planar. Comparison with the experimental spin densities and the fine structure constants D and E in the triplet state point to slightly weaker correlations than assumed by the PPP model. The introduction of a 1-8 bond to mimic poly(paraphenylene)s gives an optical gap that is in good agreement with experiment.

Tailoring the Magnetic and Optical Characteristics of Nanocrystalline BiFeO3 by Ce Doping

The Ce-doped BiFeO3 (BFO) nanoparticles (NPs) were synthesized using a facile solgel route with varying Ce concentrations in the range of 15 mol%. Ferroelectric transition temperature was found to shift from 723 degrees C +/- 5 degrees C for pristine BFO NPs to 534 degrees C +/- 3 degrees C for 5 mol% Ce-doped BFO NPs. UVVis absorption spectra of BFO NPs showed a significant blue shift of similar to 100 nm on Ce doping. The Fourier transformed infrared (FTIR) spectrum centered similar to 550 cm(-1) becomes considerably broadened on Ce doping which is due to additional closely spaced vibrational peaks as revealed by the second derivative FTIR analysis. High-frequency EPR measurements indicated that clustering occurs at high dopant levels, and that Fe is present as Fe(3+)corroborating Mossbauer measurements. The values of saturation and remanent magnetization for 3% Ce-doped BFO NPs are 3.03 and 0.49 emu/g, respectively, which are quite significant at room temperature, making it more suitable for technological applications.

Structural, EPR, optical and magnetic properties of alpha-Fe2O3 nanoparticles

alpha-Fe2O3 nanoparticles were synthesized by a low temperature solution combustion method. The structural, magnetic and luminescence properties were studied. Powder X-ray diffraction (PXRD) pattern of alpha-Fe2O3 exhibits pure rhombohedral structure. SEM micrographs reveal the dumbbell shaped particles. The EPR spectrum shows an intense resonance signal at g approximate to 5.61 corresponding to isolated Fe3+ ions situated in axially distorted sites, whereas the g approximate to 2.30 is due to Fe3+ ions coupled by exchange interaction. Raman studies show A(1g) (225 cm(-1)) and E-g (293 and 409 cm(-1)) phonon modes. The absorption at 300 nm results from the ligand to metal charge transfer transitions whereas the 540 nm peak is mainly due to the (6)A(1) + (6)A(1) —> T-4(1)(4G) + T-4(1)(4G) excitation of an Fe3+-Fe3+ pair. A prominent TL glow peak was observed at 140 C at heating rate of 5 degrees C s(-1). The trapping parameters namely activation energy (E), frequency factor (s) and order of kinetics (b) were evaluated and discussed. (C) 2012 Elsevier B.V. All rights reserved.

Rapid, microwave-assisted synthesis of Gd2O3 and Eu:Gd2O3 nanocrystals: characterization, magnetic, optical and biological studies

Ultra-small crystals of undoped and Eu-doped gadolinium oxide (Gd2O3) were synthesised by a simple, rapid microwave-assisted route, using benzyl alcohol as the reaction solvent. XRD, XPS and TEM analysis reveal that the as-prepared powder material consists of nearly monodisperse Gd2O3 nanocrystals with an average diameter of 5.2 nm. The nanocrystals show good magnetic behaviour and exhibit a larger reduction in relaxation time of water protons than the standard Gd-DTPA complex currently used in MRI imaging. Cytotoxicity studies (both concentration- and time-dependent) of the Gd2O3 nanocrystals show no adverse effect on cell viability, evidencing their high biological compatibility. Finally, Eu:Gd2O3 nanocrystals were prepared by a similar route and the red luminescence of Eu3+ activator ions was used to study the cell permeability of the nanocrystals. Red fluorescence from Eu3+ ions observed by fluorescence microscopy shows that the nanocrystals (Gd2O3 and Eu:Gd2O3) can permeate not only the cell membrane but can also enter the cell nucleus, rendering them candidate materials not only for MRI imaging but also for drug delivery when tagged or functionalized with specific drug molecules.