Investigation on non-exchange spring behaviour and exchange spring behaviour: A first order reversal curve analysis

The First Order Reversal Curve (FORC) method has been utilised to understand the magnetization reversal and the extent of the irreversible magnetization of the soft CoFe2O4-hard SrFe12O19 nanocomposite in the nonexchange spring and the exchange spring regime. The single peak switching behaviour in the FORC distribution of the exchange spring composite confirms the coherent reversal of the soft and hard phases. The onset of the nucleation field and the magnetization reversal by domain wall movement are also evident from the FORC measurements. (C) 2013 AIP Publishing LLC.

Dynamics of H-atom exchange in stable cis-dihydrogen/hydride complexes of ruthenium( II) bearing phosphine and N-N bidentate ligands

Synthesis and characterization of cis, trans-RuH(eta(2)-H-2)(PPh3)(2)(N-N)]OTf] (N-N = 2,2'-bipyridyl (bpy) 1a, 2,2'-bipyrimidine (bpm) 2a; OTf = trifluoromethane sulfonate (CF3SO3)) complexes are reported. The cis-H-2/hydride ligands are involved in H-atom site exchange between the two moieties. This dynamics was investigated by variable temperature NMR spectral studies based on which the mechanism of the exchange process was deduced. The Delta G(#) for the exchange of H-atoms between the eta(2)-H-2 and hydride ligands was determined to be around 8 and 13 kJ mol(-1), respectively, for 1a and 2a. The H-H distances (d(HH), A) in complexes 1a and 2a have been calculated from the T-1(minimum) and (1)J(H, D) and are found to be 1.07 A (slow) and 0.95 A for 1a and 1.04 A (slow) and 0.94 A for 2a, respectively. The molecular structure of 1a was determined by X-ray crystallography.

Kinetically stabilized C-60-toluene solvate nanostructures with a discrete absorption edge enabling supramolecular topotactic molecular exchange

Nanosized fullerene solvates have attracted widespread research attention due to recent interesting discoveries. A particular type of solvate is limited to a fixed number of solvents and designing new solvates within the same family is a fundamental challenge. Here we demonstrate that the hexagonal closed packed (HCP) phase of C-60 solvates, formed with m-xylene, can also be stabilized using toluene. Contrary to the notion on their instability, these can be stabilized from minutes up to months by tuning the occupancy of solvent molecules. Due to high stability, we could record their absorption edge, and measure excitonic life-time, which has not been reported for any C-60 solvate. Despite being solid, absorbance spectrum of the solvates is similar in appearance to that of C-60 in solution. A new absorption band appears at 673 nm. The fluorescence lifetime at 760 nm is similar to 1.2 ns, suggesting an excited state unaffected by solvent-C-60 interaction. Finally, we utilized the unstable set of HCP solvates to exchange with a second solvent by a topotactic exchange mechanism, which rendered near permanent stability to the otherwise few minutes stable solvates. This is also the first example of topotactic exchange in supramolecular crystal, which is widely known in ionic solids. (C) 2014 Elsevier Ltd. All rights reserved.

Seeded-growth, nanocrystal-fusion, ion-exchange and inorganic-ligand mediated formation of semiconductor-based colloidal heterostructured nanocrystals

This article highlights different synthetic strategies for the preparation of colloidal heterostructured nanocrystals, where at least one component of the constituent nanostructure is a semiconductor. Growth of shell material on a core nanocrystal acting as a seed for heterogeneous nucleation of the shell has been discussed. This seeded-growth technique, being one of the most heavily explored mechanisms, has already been discussed in many other excellent review articles. However, here our discussion has been focused differently based on composition (semiconductor@semiconductor, magnet@semiconductor, metal@semiconductor and vice versa), shape anisotropy of the shell growth, and synthetic methodology such as one-step vs. multi-step. The relatively less explored strategy of preparing heterostructures via colloidal sintering of different nanostructures, known as nanocrystal-fusion, has been reviewed here. The ion-exchange strategy, which has recently attracted huge research interest, where compositional tuning of nanocrystals can be achieved by exchanging either the cation or anion of a nanocrystal, has also been discussed. Specifically, controlled partial ion exchange has been critically reviewed as a viable synthetic strategy for the fabrication of heterostructures. Notably, we have also included the very recent methodology of utilizing inorganic ligands for the fabrication of heterostructured colloidal nanocrystals. This unique strategy of inorganic ligands has appeared as a new frontier for the synthesis of heterostructures and is reviewed in detail here for the first time. In all these cases, recent developments have been discussed with greater detail to add upon the existing reviews on this broad topic of semiconductor-based colloidal heterostructured nanocrystals.

Stabilization of Co-3 - Oxoclusters in a pcu Net: Synthesis, Structure, Solvent Exchange (Single Crystal to Single Crystal) and Magnetic Studies

The solvothermal reaction of CoCl(2)4H(2)O and 4,4-sulfonyldibenzoic acid (H(2)SDBA) resulted in the formation of a three-dimensional coordination polymer Co-3(C14H8O6S)(3)(DMA)(2)(MeOH)].DMA (Ia) consisting of trinuclear Co-3 oxo-cluster units. The Co-3 trimeric units are connected by SDBA(2-) anions leading to a three dimensional structure with a pcu topology. The terminal methanol molecules could be exchanged in a single crystal to single crystal (SCSC) fashion by other similar solvent molecules (ethanol, acetonitrile, water, ethyleneglycol). Magnetic studies on the parent compound, Ia, indicate antiferromagnetic interactions between the central metal atoms.

Exchange bias in strained SrRuO3 thin films

Recently, it was found that the ferromagnetic SrRuO3 when combined with another ferromagnet in thin film form gives rise to exchange bias (EB) effect. However, we observed EB in single, strained, SrRuO3 thin films grown on diamagnetic LaAlO3 (100) substrates. It displays the training effect, which essentially confirms EB. The temperature dependence of the EB reveals the blocking temperature to be around similar to 75 K. The strength of the exchange bias decreases with the increase in thickness of the film. We observe tensile strain in the out of plane direction. Further, the presence of in-plane compressive strain is observed through asymmetric reciprocal space mapping. Finally, we find a direct link between strain and EB. The evolution of strain with thickness matches well with the nature of scaled EB. It has been shown earlier by first principle calculations that this strain can induce EB in thin films. (C) 2014 AIP Publishing LLC.

Long-Term Sustained Release of Salicylic Acid from Cross-Linked Biodegradable Polyester Induces a Reduced Foreign Body Response in Mice

There has been a continuous surge toward developing new biopolymers that exhibit better in vivo biocompatibility properties in terms of demonstrating a reduced foreign body response (FBR). One approach to mitigate the undesired FBR is to develop an implant capable of releasing anti-inflammatory molecules in a sustained manner over a long time period. Implants causing inflammation are also more susceptible to infection. In this article, the in vivo biocompatibility of a novel, biodegradable salicylic acid releasing polyester (SAP) has been investigated by subcutaneous implantation in a mouse model. The tissue response to SAP was compared with that of a widely used biodegradable polymer, poly(lactic acid-co-glycolic acid) (PLGA), as a control over three time points: 2, 4, and 16 weeks postimplantation. A long-term in vitro study illustrates a continuous, linear (zero order) release of salicylic acid with a cumulative mass percent release rate of 7.34 x 10(-4) h(-1) over similar to 1.5-17 months. On the basis of physicochemical analysis, surface erosion for SAP and bulk erosion for PLGA have been confirmed as their dominant degradation modes in vivo. On the basis of the histomorphometrical analysis of inflammatory cell densities and collagen distribution as well as quantification of proinflammatory cytokine levels (TNF-alpha and IL-1 beta), a reduced foreign body response toward SAP with respect to that generated by PLGA has been unambiguously established. The favorable in vivo tissue response to SAP, as manifest from the uniform and well-vascularized encapsulation around the implant, is consistent with the decrease in inflammatory cell density and increase in angiogenesis with time. The above observations, together with the demonstration of long-term and sustained release of salicylic acid, establish the potential use of SAP for applications in improved matrices for tissue engineering and chronic wound healing.

Insights into the Functional Roles of N-Terminal and C-Terminal Domains of Helicobacter pylori DprA

DNA processing protein A (DprA) plays a crucial role in the process of natural transformation. This is accomplished through binding and subsequent protection of incoming foreign DNA during the process of internalization. DprA along with Single stranded DNA binding protein A (SsbA) acts as an accessory factor for RecA mediated DNA strand exchange. H. pylori DprA (HpDprA) is divided into an N-terminal domain and a C-terminal domain. In the present study, individual domains of HpDprA have been characterized for their ability to bind single stranded (ssDNA) and double stranded DNA (dsDNA). Oligomeric studies revealed that HpDprA possesses two sites for dimerization which enables HpDprA to form large and tightly packed complexes with ss and dsDNA. While the N-terminal domain was found to be sufficient for binding with ss or ds DNA, C-terminal domain has an important role in the assembly of poly-nucleoprotein complex. Using site directed mutagenesis approach, we show that a pocket comprising positively charged amino acids in the N-terminal domain has an important role in the binding of ss and dsDNA. Together, a functional cross talk between the two domains of HpDprA facilitating the binding and formation of higher order complex with DNA is discussed.

Exchange spring behaviour in SrFe12O19-CoFe2O4 nanocomposites

Nanocomposites of hard (SrFe12O19) and soft ferrite (CoFe2O4) are prepared by mixing individual ferrite components at appropriate weight ratio and subsequent heat treatment. The magnetization of the composites showed hysteresis loop that is characteristic of the exchange spring system. The variation of J(r)/J(r)(infinity) vs. J(d)/J(r)(infinity) for these nanocomposites are investigated to understand the presence of both the interacting field and the disorder in the system. This is further corroborated with the First Order Reversal Curve analysis (FORC) on the nanocomposites of 1:4 (Cobalt Ferrite: Strontium Ferrite) and 1:16 (Cobalt Ferrite: Strontium Ferrite). The FORC distribution reveals that the pinning mechanism is stronger in the nanocomposite of 1:4 compared to 1:16. However, the nanocomposite of 1:16 exhibit superior exchange coupling strength in contrast to 1:4. The asymmetric nature of the FORC distribution at H-c = 0 Oe for both the nanocomposites validates the intercoupling between the reversible and irreversible magnetization. (C) 2015 Author(s).

Structural diversities in Cu(I) and Ag(I) sulfonate coordination polymers and their anion exchange properties

Two new Cu(I) compounds, namely Cu-2(bds)(bpy)(2)]center dot 2H(2)O (1) and Cu-4(bds)(2)(azpy)(4)]center dot 6H(2)O (3) (where bds = benzene-1,3-disulfonate, bpy = 4,4'-bipyridine and azpy = 4,4'-azopyridine), and four Ag(I) compounds, namely Ag-2(bds)(bpy)(2)]center dot 2H(2)O (2), Ag-2(bds)(azpy)(2)]center dot 4H(2)O (4), Ag(bds)(1/2)(bpe)]center dot 3H(2)O (5), and Ag-4(bds)(2)(tmdp)(4)]center dot 9H(2)O (6) (where bpe = 1,2-di(4-pyridyl) ethylene and tmdp = 4,4'trimethylenedipyridine), have been synthesized, and their structures were determined and characterized by elemental analysis, IR, UV-vis and thermal studies. The structure of the compounds changed from 1D (1 and 2) to 2D (3-5) and interpenetrated 3D (6). In the case of 5, a solid-state 2 + 2] photochemical cycloaddition reaction has been performed. Compound 2 exhibits a reversible anion exchange for perchlorate and permanganate, whereas the other compounds (1, 3-6) exhibit an irreversible anion exchange behaviour for perchlorate. Catalytic studies on 2 indicate Lewis acidity.

Experimental Analysis of Water Vapor Diffusion Through Porous Membranes in a Proton Exchange Membrane Fuel Cell

We report the diffusion characteristics of water vapor through two different porous media, viz., membrane electrode assembly (MEA) and gas diffusion layer (GDL) in a nonoperational fuel cell. Tunable diode laser absorption spectroscopy (TDLAS) was employed for measuring water vapor concentration in the test channel. Effects of the membrane pore size and the inlet humidity on the water vapor transport are quantified through mass flux and diffusion coefficient. Water vapor transport rate is found to be higher for GDL than for MEA. The flexibility and wide range of application of TDLAS in a fuel cell setup is demonstrated through experiments with a stagnant flow field on the dry side.

Study of H/D exchange rates to derive the strength of intramolecular hydrogen bonds in halo substituted organic building blocks: An NMR spectroscopic investigation

Rates of hydrogen/deuterium (H/D) exchange determined by H-1 NMR spectroscopy are utilized to derive the strength of hydrogen bonds and to monitor the electronic effects in the site-specific halogen substituted benzamides and anilines. The theoretical fitting of the time dependent variation of the integral areas of H-1 NMR resonances to the first order decay function permitted the determination of HID exchange rate constants (k) and their precise half-lives (t(1/2)) with high degree of reproducibility. The comparative study also permitted the unambiguous determination of relative strength of hydrogen bonds and the contribution from electronic effects on the HID exchange rate. (C) 2015 Elsevier B.V. All rights reserved.

Investigation on the origin of exchange bias in epitaxial, oriented and polycrystalline Fe3O4 thin films

We observe exchange bias (EB) in a single magnetic film Fe3O4 at temperature T < 200 K. Irrespective of crystallographic orientations of grown Fe3O4; they exhibit similar nature of EB for (100) epitaxial, (111) oriented and polycrystalline Fe3O4 thin films. Growth induced defects such as anti-phase boundaries (APBs) in epitaxial Fe3O4 thin film is known to have an influence on the magnetic interaction. But, it is noticed that according to the common consensus of APBs alone cannot explain the origin of EB. If majority of APBs end up with mainly anti-ferromagnetic interactions across these boundaries together with the internal ordering modification in Fe3O4, then EB can emerge at low temperatures. Hence, we propose the idea of directional anti-ferromagnetic APB induced EB in Fe3O4 triggered by internal ordering for T <= 200 K. Similar arguments are extended to (111) oriented as well as polycrystalline Fe3O4 films where the grain boundaries can impart same consequence as that of APBs. (C) 2015 Author(s).

Effect of Super-exchange Interaction on Ground state Magnetic Properties of Spin-dependent Falicov-Kimball Model on a Triangular Lattice

Ground state magnetic properties are studied by incorporating the super-exchange interaction (J(se)) in the spin-dependent Falicov-Kimball model (FKM) between localized (f-) electrons on a triangular lattice for half filled case. Numerical diagonalization and Monte-Carlo simulation are used to study the ground state magnetic properties. We have found that the magnetic moment of (d-) and (f-) electrons strongly depend on the value of Hund's exchange (J), super-exchange interaction (J(se)) and also depends on the number of (d-) electrons (N-d). The ground state changes from antiferromagnetic (AFM) to ferromagnetic (FM) state as we decrease (N-d). Also the density of d electrons at each site depends on the value of J and J(se).