Adjusting the Néel relaxation time of Fe3O4/Zn x Co1-x Fe2O4 core/shell nanoparticles for optimal heat generation in magnetic hyperthermia.

In this work it is shown a precise way to optimize the heat generation in high viscosity magnetic colloids, by adjusting the Néel relaxation time in core/shell bimagnetic nanoparticles, for magnetic fluid hyperthermia (MFH) applications. To pursue this goal, Fe3O4/Zn x Co1-x Fe2O4 core/shell nanoparticles were synthesized with 8.5 nm mean core diameter, encapsulated in a shell of ∼1.1 nm of thickness, where the Zn atomic ratio (Zn/(Zn + Co) at%) changes from 33 to 68 at%. The magnetic measurements are consistent with a rigid interface coupling between the core and shell phases, where the effective magnetic anisotropy systematically decreases when the Zn concentration increases, without a significant change of the saturation magnetization. Experiments of MFH of 0.1 wt% of these particles dispersed in water, in Dulbecco modified Eagles minimal essential medium, and a high viscosity butter oil, result in a large specific loss power (SLP), up to 150 W g-1, when the experiments are performed at 571 kHz and 200 Oe. The SLP was optimized adjusting the shell composition, showing a maximum for intermediate Zn concentration. This study shows a way to maximize the heat generation in viscous media like cytosol, for those biomedical applications that require smaller particle sizes.

Adjusting the Néel relaxation time of Fe3O4/ZnxCo1-xFe2O4 core/shell nanoparticles for optimal heat generation in magnetic hyperthermia.

In this work it is shown a precise way to optimize the heat generation in high viscosity magnetic colloids, by adjusting the Néel relaxation time in core/shell bimagnetic nanoparticles, for Magnetic Fluid Hyperthermia applications. To pursue this goal, Fe3O4/ZnxCo1-xFe2O4 core/shell nanoparticles were synthesized with 8.5 nm mean core diameter, encapsulated in a shell of ~1.1 nm of thickness, where the Zn atomic ratio (Zn/(Zn+Co) at%) changes from 33 at% to 68 at%. The magnetic measurements are consistent with a rigid interface coupling between the core and shell phases, where the effective magnetic anisotropy systematically decreases when the Zn concentration increases, without a significant change of the saturation magnetization. Experiments of magnetic fluid hyperthermia of 0.1 wt% of these particles dispersed in water, DMEM (Dulbecco modified Eagles minimal essential medium) and a high viscosity butter oil, result in a large specific loss power (SLP), up to 150 W/g, when the experiments are performed at 571 kHz and 200 Oe. The SLP was optimized adjusting the shell composition, showing a maximum for intermediate Zn concentration. This study shows a way to maximize the heat generation in viscous media like cytosol, for those biomedical applications that requiere smaller particle sizes .

Microwave Photon Detectors Based on Semiconducting Double Quantum Dots.

Detectors of microwave photons find applications in different fields ranging from security to cosmology. Due to the intrinsic difficulties related to the detection of vanishingly small energy quanta ℏ ω , significant portions of the microwave electromagnetic spectrum are still uncovered by suitable techniques. No prevailing technology has clearly emerged yet, although different solutions have been tested in different contexts. Here, we focus on semiconductor quantum dots, which feature wide tunability by external gate voltages and scalability for large architectures. We discuss possible pathways for the development of microwave photon detectors based on photon-assisted tunneling in semiconducting double quantum dot circuits. In particular, we consider implementations based on either broadband transmission lines or resonant cavities, and we discuss how developments in charge sensing techniques and hybrid architectures may be beneficial for the development of efficient photon detectors in the microwave range.

Magnetic Nanoparticles Coated with (R)-9-Acetoxystearic Acid for Biomedical Applications.

The well-known ability to selectively drive nanomagnetic materials coated with anticancer drugs into tumor cells suggested the synthesis and the characterization of magnetic nanoparticles (MNPs) functionalized with (R)-9-acetoxystearic acid, the acetic ester of (R)-9-hydroxystearic acid (9-HSA), an antiproliferative agent active against different cancer cells. The acyl chloride of (R)-9-acetoxystearic acid, synthesized in two steps from 9-HSA, was reacted with (3-aminopropyl)triethoxysilane, chosen as a linker between MNPs and the stearyl moiety. In the last step, the novel amide was bound to magnetite NPs by reaction with silyl groups. A detailed structural, chemical, and magnetic characterization of the obtained material proved that it possesses properties in agreement with the requirements for drug delivery, opening the possibility to further insights focused on the 9-HSA biomedical applications.

Microwave-Assisted Tunneling in Hard-Wall InAs/InP Nanowire Quantum Dots.

With downscaling of electronic circuits, components based on semiconductor quantum dots are assuming increasing relevance for future technologies. Their response under external stimuli intrinsically depend on their quantum properties. Here we investigate single-electron tunneling in hard-wall InAs/InP nanowires in the presence of an off-resonant microwave drive. Our heterostructured nanowires include InAs quantum dots (QDs) and exhibit different tunnel-current regimes. In particular, for source-drain bias up to few mV Coulomb diamonds spread with increasing contrast as a function of microwave power and present multiple current polarity reversals. This behavior can be modelled in terms of voltage fluctuations induced by the microwave field and presents features that depend on the interplay of the discrete energy levels that contribute to the tunneling process.

Coherent Spin Dynamics in Molecular Cr8Zn Wheels.

Controlling and understanding transitions between molecular spin states allows selection of the most suitable ones for qubit encoding. Here we present a detailed investigation of single crystals of a polynuclear Cr8Zn molecular wheel using 241 GHz electron paramagnetic resonance (EPR) spectroscopy in high magnetic field. Continuous wave spectra are well reproduced by spin Hamiltonian calculations, which evidence that transitions in correspondence to a well-defined anticrossing involve mixed states with different total spin. We studied, by means of spin echo experiments, the temperature dependence of the dephasing time (T2) down to 1.35 K. These results are reproduced by considering both hyperfine and intermolecular dipolar interactions, evidencing that the dipolar contribution is completely suppressed at the lowest temperature. Overall, these results shed light on the effects of the decoherence mechanisms, whose understanding is crucial to exploit chemically engineered molecular states as a resource for quantum information processing.

Electronic Structure of a Mixed-Metal Fluoride-Centered Triangle Complex: A Potential Qubit Component.

A novel fluoride-centered triangular-bridged carboxylate complex, [Ni2Cr(µ3-F)(O2C(t)Bu)6(HO2C(t)Bu)3] (1), is reported. Simple postsynthetic substitution of the terminal pivalic acids in 1 with pyridine and 4-methylpyridine led to the isolation of [Ni2Cr(µ3-F)(O2C(t)Bu)6(C5H5N)3] (2) and [Ni2Cr(µ3-F)(O2C(t)Bu)6((4-CH3)C5H4N)3] (3). Structural and magnetic characterizations carried out on the series reveal a dominating antiferromagnetic interaction between the nickel and chromium centers leading to an S = (1)/2 ground state with a very unusual value of geff = 2.48.

Effects of the Dzyaloshinskii-Moriya interaction in Cr3 triangular spin clusters detected by specific heat and multi-frequency electron spin resonance.

An oxo-centered [Cr3O(O2C(t)Bu)6(H2O)3](O2C(t)Bu) HO2C(t)Bu·2EtOH triangular cluster has been synthesized and its magnetic properties have been studied by means of complementary techniques, namely magnetometry, specific heat and multi-frequency Electron Paramagnetic Resonance (EPR). Measurements on oriented single-crystals evidenced the presence of anisotropy that we attributed to the combined effect of Dzyaloshinskii-Moriya exchange interaction and distortion. By means of a minimal set of parameters, we show that a simple analytical model well describes the main features of the full set of experimental data.

Low temperature magnetic properties and spin dynamics in single crystals of Cr8Zn antiferromagnetic molecular rings.

A detailed experimental investigation of the effects giving rise to the magnetic energy level structure in the vicinity of the level crossing (LC) at low temperature is reported for the open antiferromagnetic molecular ring Cr8Zn. The study is conducted by means of thermodynamic techniques (torque magnetometry, magnetization and specific heat measurements) and microscopic techniques (nuclear magnetic resonance line width, nuclear spin lattice, and spin-spin relaxation measurements). The experimental results are shown to be in excellent agreement with theoretical calculations based on a minimal spin model Hamiltonian, which includes a Dzyaloshinskii-Moriya interaction. The first ground state level crossing at µ0Hc1 = 2.15 T is found to be an almost true LC while the second LC at µ0Hc2 = 6.95 T has an anti-crossing gap of Δ12 = 0.19 K. In addition, both NMR and specific heat measurements show the presence of a level anti-crossing between excited states at µ0H = 4.5 T as predicted by the theory. In all cases, the fit of the experimental data is improved by introducing a distribution of the isotropic exchange couplings (J), i.e., using a J strain model. The peaks at the first and second LCs in the nuclear spin-lattice relaxation rate are dominated by inelastic scattering and a value of Γ âˆ¼ 10(10) rad/s is inferred for the life time broadening of the excited state of the open ring, due to spin phonon interaction. A loss of NMR signal (wipe-out effect) is observed for the first time at LC and is explained by the enhancement of the spin-spin relaxation rate due to the inelastic scattering.

Octanuclear [Ni(II)4Ln(III)4] complexes. Synthesis, crystal structures and magnetocaloric properties.

Two original heterooctanuclear [Ni(II)4Ln(III)4] complexes (Ln(III) = Sm(III), Gd(III)) have been obtained starting from the [Ni(II)(valpn)(H2O)2] mononuclear precursor [H2valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol)] and the corresponding lanthanide nitrates, in the presence of azide anions, through slow capture of atmospheric CO2. Three weak and competitive exchange interactions, J(GdGd), J(GdNi), J(NiNi), make the ground state of this magnetic system degenerate at cryogenic temperature and zero field. This, along with the high spin of Gd(III), lead to a significant magnetocaloric effect spread in the temperature range 1 to 20 K (ΔSm[0-7 T, 3.5 K] = 19 J kg(-1) K(-1)).

Synthesis and magnetothermal properties of a ferromagnetically coupled Ni(II)-Gd(III)-Ni(II) cluster.

A linear trimeric cluster of molecular formula [Ni2Gd(L(-))6](NO3) (1) (L(-) = (C14H12NO2) has been isolated with its structure determined via single crystal X-ray diffraction. Magnetic susceptibility measurements of 1 show that the nickel and gadolinium ions are coupled ferromagnetically, with a ground total spin state (S) of 11/2. Best fit spin Hamiltonian parameters obtained for 1 are J(1(Ni-Gd)) = +0.54 cm(-1), g = 2.01. EPR measurements confirm a low magnetic anisotropy (D = -0.135 cm(-1)) for 1. Heat capacity determination of the magnetocaloric effect (MCE) parameters for 1 shows that the change in magnetic entropy (-ΔS(m)) achieves a maximum of 13.74 J kg(-1) K(-1) at 4.0 K, with the ferromagnetic coupling giving a rapid change in low applied fields, confirming the potential of Gd molecular derivatives as coolants at liquid helium temperature.

Magnetic cooling at a single molecule level: a spectroscopic investigation of isolated molecules on a surface.

A sub-monolayer distribution of isolated molecular Fe14 (bta)6 nanomagnets is deposited intact on a Au(111) surface and investigated by X-ray magnetic circular dichroism spectroscopy. The entropy variation with respect to the applied magnetic field is extracted from the magnetization curves and evidences high magnetocaloric values at the single molecule level.

Studies of hybrid organic-inorganic [2] and [3]rotaxanes bound to Au surfaces.

Hybrid organic-inorganic [2]- and [3]rotaxanes have been synthesised, and their ability to bind to Au surfaces studied; the length of the tethering group is found to control how the supramolecular assembly binds to the surface and we find that [2]rotaxanes show improved stability over previous studies of simple inorganic rings.

Controlled positioning of nanoparticles on graphene by noninvasive AFM lithography.

Atomic force microscopy is shown to be an excellent lithographic technique to directly deposit nanoparticles on graphene by capillary transport without any previous functionalization of neither the nanoparticles nor the graphene surface while preserving its integrity and conductivity properties. Moreover this technique allows for (sub)micrometric control on the positioning thanks to a new three-step protocol that has been designed with this aim. With this methodology the exact target coordinates are registered by scanning the tip over the predetermined area previous to its coating with the ink and deposition. As a proof-of-concept, this strategy has successfully allowed the controlled deposition of few nanoparticles on 1 µm(2) preselected sites of a graphene surface with high accuracy.

Dodecanuclear [Cu(II)6Gd(III)6] nanoclusters as magnetic refrigerants.

A novel dodecanuclear complex, [{(HL)(L)(DMF)Cu(II)Gd(III)(DMF)(H(2)O)}(6)]·6DMF (1; DMF = N,N-dimethylformamide), has been obtained using the ligand resulting from the condensation of 3-formylsalicylic acid with hydroxylamine (H(3)L). The exchange interaction between the phenoxo-bridged Cu(II) and Gd(III) ions is weak ferromagnetic (J = +1.01 cm(-1)). The combination of a high-spin ground state with small anisotropy leads to a significant magnetocaloric effect [-ΔS(m)(0-7 T) = 23.5 J K g(-1) K(-1) at ∼2 K].

Self-assembled monolayer of Cr7Ni molecular nanomagnets by sublimation.

We show, by complementary spectroscopic and STM analysis, that Cr(7)Ni derivatives are suitable to be sublimed in UHV conditions. Cr(7)Ni-bu weakly bonds to gold surface and can diffuse relatively freely on it, forming monolayers with hexagonal 2D packing. Conversely, by adding a functional thiol group to the central dibutylamine, a covalent bond between the molecule and surface gold adatoms is promoted, leading to a strong molecular grafting and the formation of a disordered monolayer. These two examples demonstrate the possibility to control the assembly of a large molecular complex, as rationalized by DFT calculations that establish different energy scales in the deposition processes. Moreover, low-temperature XMCD sprectra show that the magnetic features of Cr(7)Ni rings deposited in UHV on gold remain unchanged with respect to those of the corresponding bulk sample.

Grafting molecular Cr7Ni rings on a gold surface.

Molecular {Cr(7)Ni} rings have shown several ideal features for the observation of quantum phenomena and they appear suitable candidates for qubits encoding at low temperatures. We have exploited different functionalization pathways to graft molecular {Cr(7)Ni} rings onto a Au(111) surface from the liquid phase and here we report a comparative analysis of the results obtained by STM, XPS, XAS and XMCD experimental techniques.

Engineering the coupling between molecular spin qubits by coordination chemistry.

The ability to assemble weakly interacting subsystems is a prerequisite for implementing quantum information processing and generating controlled entanglement. In recent years, molecular nanomagnets have been proposed as suitable candidates for qubit encoding and manipulation. In particular, antiferromagnetic Cr7Ni rings behave as effective spin-1/2 systems at low temperature and show long decoherence times. Here, we show that these rings can be chemically linked to each other and that the coupling between their spins can be tuned by choosing the linker. We also present calculations that demonstrate how realistic microwave pulse sequences could be used to generate maximally entangled states in such molecules.

Magnetic imaging of cyanide-bridged co-ordination nanoparticles grafted on FIB-patterned Si substrates.

Prussian blue CsNiCr nanoparticles are used to decorate selected portions of a Si substrate. For successful grafting to take place, the Si surface needs first to be chemically functionalized. Low-dose focused ion beam patterning on uniformly functionalized surfaces selects those portions that will not participate in the grafting process. Step-by-step control is assured by atomic force and high-resolution scanning electron microscopy, revealing a submonolayer distribution of the grafted nanoparticles. By novel scanning Hall-probe microscopy, an in-depth investigation of the magnetic response of the nanoparticles to varying temperature and applied magnetic field is provided. The magnetic images acquired suggest that low-temperature canted ferromagnetism is found in the grafted nanoparticles, similar to what is observed in the equivalent bulk material.

Molecular routes for spin cluster qubits.

We report on real molecular complexes and propose strategies that explore the possibility of implementation of specific quantum computation architectures with molecular spin systems. We focus on Cr3+ carboxylate derivatives and use the Loss-DiVincenzo scheme as reference.