Dynamic Internal Cavities of Dendrimers as Constrained Media. A Study of Photochemical Isomerizations of Stilbene and Azobenzene Using Poly(alkyl aryl ether) Dendrimers

Dendritic rnicroenvironments defined by dynamic internal cavities of a dendrimer were probed through geometric isomerization of stilbene and azobenzene. A third-generation poly(alkyl aryl ether) dendrimer with hydrophilic exterior and hydrophobic interior was used as a reaction cavity in aqueous medium. The dynamic inner cavity sizes were varied by utilizing alkyl linkers that connect the branch junctures from ethyl to n-pentyl moiety (C(2)G(3)-C(5)G(3)). Dendrimers constituted with n-pentyl linker were found to afford higher solubilities of stilbene and azobenzene. Direct irradiation of trans-stilbene showed that C(5)G(3) and C(4)G(3) dendrimers afforded considerable phenanthrene formation, in addition to cis-stilbene, whereas C(3)G(3) and C(2)G(3) gave only cis-stilbene. An electron-transfer sensitized trans-cis isomerization, using cresyl violet perchlorate as the sensitizer, also led to similar results. Thermal isomerization of cis-azobenzene to trans-azobenzene within dendritic microenvironments revealed that the activation energy of the cis- to trans-isomer was increasing in the series C(5)G(3) < C(4)G(3) < C(3)G(3)

Cyclodextrin functionalized magnetic iron oxide nanocrystals: a host-carrier for magnetic separation of non-polar molecules and arsenic from aqueous media

A single-step magnetic separation procedure that can remove both organic pollutants and arsenic from contaminated water is clearly a desirable goal. Here we show that water dispersible magnetite nanoparticles prepared by anchoring carboxymethyl-beta-cyclodextrin (CMCD) cavities to the surface of magnetic nanoparticles are suitable host carriers for such a process. Monodisperse, 10 nm, spherical magnetite, Fe3O4, nanocrystals were prepared by the thermal decomposition of FeOOH. Trace amounts of antiferromagnet, FeO, present in the particles provides an exchange bias field that results in a high superparamagnetic blocking temperature and appreciable magnetization values that facilitate easy separation of the nanocrystals from aqueous dispersions on application of modest magnetic fields. We show here that small molecules like naphthalene and naphthol can be removed from aqueous media by forming inclusion complexes with the anchored cavities of the CMCD-Fe3O4 nanocrystals followed by separation of the nanocrystals by application of a magnetic field. The adsorption properties of the iron oxide surface towards As ions are unaffected by the CMCD capping so it too can be simultaneously removed in the separation process. The CMCD-Fe3O4 nanocrystals provide a versatile platform for magnetic separation with potential applications in water remediation.

A spring-mass-lever model, stiffness and inertia maps for single-input, single-output compliant mechanisms

A spring-mass-lever (SML) model is introduced in this paper for a single-input-single-output compliant mechanism to capture its static and dynamic behavior. The SML model is a reduced-order model, and its five parameters provide physical insight and quantify the stiffness and inertia(1) at the input and output ports as well as the transformation of force and displacement between the input and output. The model parameters can be determined with reasonable accuracy without performing dynamic or modal analysis. The paper describes two uses of the SML model: computationally efficient analysis of a system of which the compliant mechanism is a part; and design of compliant mechanisms for the given user-specifications. During design, the SML model enables determining the feasible parameter space of user-specified requirements, assessing the suitability of a compliant mechanism to meet the user-specifications and also selecting and/or re-designing compliant mechanisms from an existing database. Manufacturing constraints, material choice, and other practical considerations are incorporated into this methodology. A micromachined accelerometer and a valve mechanism are used as examples to show the effectiveness of the SML model in analysis and design. (C) 2012 Published by Elsevier Ltd.

Ratiometric, reversible, and parts per billion level detection of multiple toxic transition metal ions using a single probe in micellar media

We present the selective sensing of multiple transition metal ions in water using a synthetic single probe. The probe is made up of pyrene and pyridine as signaling and interacting moiety, respectively. The sensor showed different responses toward metal ions just by varying the medium of detection. In organic solvent (acetonitrile), the probe showed selective detection of Hg2+ ion. In water, the fluorescence quenching was observed with three metal ions, Cu2+, Hg2+, and Ni2+. Further, just by varying the surface charge on the micellar aggregates, the probe could detect and discriminate the above-mentioned three different toxic metal ions appropriately. In neutral micelles (Brij 58), the probe showed a selective interaction with Hg2+ ion as observed in acetonitrile medium. However, in anionic micellar medium (sodium dodecyl sulfate, SDS), the probe showed changes with both Cu2+ and Ni2+. under UV-vis absorption spectroscopy. The discrimination between these two ions was achieved by recording their emission spectra, where it showed selective quenching with Cu2+.

Electronic energy transfer between long-range resonance states of 3-mercaptopropionic acid capped CdTe quantum dots in aqueous media

We demonstrate electronic energy transfer between resonance states of 2 and 2.8 nm CdTe quantum dots in aqueous media using steady-state photoluminescence spectroscopy without using any external linker molecule. With increasing concentration of larger dots, there is subsequent quenching of luminescence in smaller dots accompanied by the enhancement of luminescence in larger dots. Our experimental evidence suggests that there is long-range resonance energy transfer among electronic excitations, specifically from the electronically confined states of the smaller dots to the higher excited states of the larger dots.

``On-the-fly'' kinetics of enzymatic racemization using deuterium NMR in DNA-based chiral oriented media

We report the in situ and real-time monitoring of the interconversion of L- and D-alanine-d(3) by alanine racemase from Bacillus stearothermophilus directly observed by H-2 NMR spectroscopy in anisotropic phase. The enantiomers are distinguished by the difference of their H-2 quadrupolar splittings in a chiral liquid crystal containing short DNA fragments. The proof-of-principle, the reliability, and the robustness of this new method is demonstrated by the determination of the turnover rates of the enzyme using the Michaelis Menten model.

Exchange-spring mechanism of soft and hard ferrite nanocomposites

The paper reports exchange-spring soft and hard ferrite nanocomposites synthesized by chemical co-precipitation with or without the application of ultrasonic vibration. The composites contained BaFe12O19 as the hard phase and CoFe2O4/MgFe2O4 as the soft phase. X-ray diffraction patterns of the samples in the optimum calcined condition indicated the presence of soft ferrites as face-centred cubic (fcc) and hard ferrites as hexagonal close packed (hcp) structure respectively. Temperature dependence of magnetization in the range of 20-700 degrees C demonstrated distinct presence of soft and hard ferrites as magnetic phases which are characterized by wide difference in magnetic anisotropy and coercivity. Exchange-spring mechanism led these nanocomposite systems to exchange-coupled, which ultimately produced convex hysteresis loops characteristic of a single-phase permanent magnet. Fairly high value of coercivity and maximum energy product were observed for the samples in the optimum calcined conditions with a maximum applied field of 1600 kA/m (2 T).

Generalized eigenvalue decomposition of the field autocorrelation in correlation diffusion of photons in turbid media

We propose a novel numerical method based on a generalized eigenvalue decomposition for solving the diffusion equation governing the correlation diffusion of photons in turbid media. Medical imaging modalities such as diffuse correlation tomography and ultrasound-modulated optical tomography have the (elliptic) diffusion equation parameterized by a time variable as the forward model. Hitherto, for the computation of the correlation function, the diffusion equation is solved repeatedly over the time parameter. We show that the use of a certain time-independent generalized eigenfunction basis results in the decoupling of the spatial and time dependence of the correlation function, thus allowing greater computational efficiency in arriving at the forward solution. Besides presenting the mathematical analysis of the generalized eigenvalue problem on the basis of spectral theory, we put forth the numerical results that compare the proposed numerical method with the standard technique for solving the diffusion equation.

Experimental Studies on the Mechanics of Cohesive Frictional Granular Media

The mechanical behaviour of cohesive-frictional granular materials is a combination of the strength pervading as intergranular friction (represented as an angle of internal friction - Phi), and the cohesion (C) between these particles. Most behavioral or constitutive models of this class of granular materials comprise of a cohesion and frictional component with no regard to the length scale i.e. from the micro structural models through the continuum models. An experimental study has been made on a model granular material, viz. angular sand with different weights of binding agents (varying degrees of cohesion) at multiple length scales to physically map this phenomenon. Cylindrical specimen of various diameters - 10, 20, 38, 100, 150 mm (and with an aspect ratio of 2) are reconstituted with 2, 4 and 8% by weight of a binding agent. The magnitude of this cohesion is analyzed using uniaxial compression tests and it is assumed to correspond to the peak in the normalized stress-strain plot. Increase in the cohesive strength of the material is seen with increasing size of the specimen. A possibility of ``entanglement'' occurring in larger specimens is proposed as a possible reason for deviation from a continuum framework.

Dynamic multi-relational Chinese restaurant process for analyzing influences on users in social media

We study the problem of analyzing influence of various factors affecting individual messages posted in social media. The problem is challenging because of various types of influences propagating through the social media network that act simultaneously on any user. Additionally, the topic composition of the influencing factors and the susceptibility of users to these influences evolve over time. This problem has not been studied before, and off-the-shelf models are unsuitable for this purpose. To capture the complex interplay of these various factors, we propose a new non-parametric model called the Dynamic Multi-Relational Chinese Restaurant Process. This accounts for the user network for data generation and also allows the parameters to evolve over time. Designing inference algorithms for this model suited for large scale social-media data is another challenge. To this end, we propose a scalable and multi-threaded inference algorithm based on online Gibbs Sampling. Extensive evaluations on large-scale Twitter and Face book data show that the extracted topics when applied to authorship and commenting prediction outperform state-of-the-art baselines. More importantly, our model produces valuable insights on topic trends and user personality trends beyond the capability of existing approaches.

New insights into designing metallacarborane based room temperature hydrogen storage media

Metallacarboranes are promising towards realizing room temperature hydrogen storage media because of the presence of both transition metal and carbon atoms. In metallacarborane clusters, the transition metal adsorbs hydrogen molecules and carbon can link these clusters to form metal organic framework, which can serve as a complete storage medium. Using first principles density functional calculations, we chalk out the underlying principles of designing an efficient metallacarborane based hydrogen storage media. The storage capacity of hydrogen depends upon the number of available transition metal d-orbitals, number of carbons, and dopant atoms in the cluster. These factors control the amount of charge transfer from metal to the cluster, thereby affecting the number of adsorbed hydrogen molecules. This correlation between the charge transfer and storage capacity is general in nature, and can be applied to designing efficient hydrogen storage systems. Following this strategy, a search for the best metallacarborane was carried out in which Sc based monocarborane was found to be the most promising H-2 sorbent material with a 9 wt.% of reversible storage at ambient pressure and temperature. (C) 2013 AIP Publishing LLC.

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.

Selective and Efficient Detection of Nitro-Aromatic Explosives in Multiple Media including Water, Micelles, Organogel, and Solid Support

Selective detection of nitro-aromatic compounds (NACs) at nanomolar concentration is achieved for the first time in multiple media including water, micelles or in organogels as well as using test strips. Mechanism of interaction of NACs with highly fluorescent p-phenylenevinylene-based molecules has been described as the electron transfer phenomenon from the electron-rich chromophoric probe to the electron deficient NACs. The selectivity in sensing is guided by the pK(a) of the probes as well as the NACs under consideration. TNP-induced selective gel-to-sol transition in THF medium is also observed through the reorganization of molecular self-assembly and the portable test trips are made successfully for rapid on-site detection purpose.

Simulations and experiments in punching spring-steel devices with sub-millimeter features

This work demonstrates the feasibility of mesoscale (100 μm to mm) punching of multiple holes of intricate shapes in metals. Analytical modeling, finite element (FE)simulation, and experimentations are used in this work. Two dimensional FE simulations in ABAQUS were done with an assumed material modeling and plane-strain condition. A known analytical model was used and compared with the ABAQUS simulation results to understand the effects of clearance between the punch and the die. FE simulation in ABAQUS was done for different clearances and corner radii at punch, die, and holder. A set of punches and dies were used to punch out a miniature spring-steel gripper. Comparison of compliant grippers manufactured by wire-cut electro discharge machining(EDM) and punching shows that realizing sharp interior and re-entrant corners by punching is not easy to achieve. Punching of circular holes with 5 mm and 2.5 mm diameter is achieved. The possibility of realizing meso-scale parts with complicated shapes through punching is demonstrated in this work; and some strategies are suggested for improvement.

Compact in-plane dual-axis spring-steel accelerometer

Presented in this paper is an improvement over a spring-steel dual-axis accelerometer that we had reported earlier.The fabrication process (which entails wire-cut electro discharge machining of easily accessible and inexpensive spring-steelfoil) and the sensing of the displacement (which is done using off-the-shelf Hall-effect sensors) remain the same. Theimprovements reported here are twofold: (i) the footprint of the packaged accelerometer is reduced from 80 mm square to 40mm square, and (ii) almost perfect de-coupling and symmetry are achieved between the two in-plane axes of the packageddevice as opposed to the previous embodiment where this was not the case. Good linearity with about 40 mV/g was measuredalong both the in-plane axes over a range of 0.1 to 1 g. The first two natural frequencies of the devices are at 30 Hz and 100Hz, respectively, as per the experiment. The highlights of this work are cost-effective processing, easy integration of the Hall-effect sensing capability on a customised printed circuit board, and inexpensive packaging without overly compromising eitherthe overall size or the sensitivity of the accelerometer. Through this work, we have reaffirmed the practicability of spring-steelaccelerometers towards the eventual goal of making it compete with micro machined silicon accelerometers in terms of sizeand performance. The cost is likely to be much lower for the spring-steel accelerometers than that of silicon accelerometers, especially when the volume of production is low and the sensor is to be used as a single packaged unit.