Tripodal Bile Acid Architectures Based on a Triarylphosphine Oxide Core Obtained by Copper-Catalysed 1,3]-Dipolar Cycloaddition: Synthesis and Preliminary Aggregation Studies

We report the synthesis and aggregation behaviour of new water-soluble, bile acid derived tripodal architectures based on a core derived from triphenylphosphine oxide. We employed the well-established copper-catalysed 1,3]-dipolar cycloaddition (CuAAC) for the construction of these tripodal molecules. The aggregation behaviour of these molecules in aqueous media was studied by different analytical methods such as dye solubilisation, dynamic light scattering, NMR and AFM. These molecular architectures also offer an additional advantage in aiding understanding of the influence of the nature of the bile acid backbone and of the configuration at the steroid C-3 position in these architectures; to the best of our knowledge this has not been reported in the literature. The unique gelation properties of the -derivatives were explained through molecular modelling studies and the mechanical behaviour of these gels was studied by rheology experiments.

Multivalent Cu-Doped ZnO Nanoparticles with Full Solar Spectrum Absorbance and Enhanced Photoactivity

Full solar spectrum absorbers are widely pursued for applications related to photocatalysis and photovoltaics. Here we report multivalent Cu-doped ZnO nanoparticles which exhibit full solar spectrum absorbance and high photoactivity. Metathesis-based, green-chemical approaches with synthesis yield of similar to 100% are used. Cu incorporation in ZnO results in an increase of average solar spectrum absorbance from a mere 0.4% to 34%. On the other hand, (Zn, Cu)0 composites result in materials with up to 64% average solar spectrum absorbance. Doped systems operate well under both visible and UV illumination. The nanomaterials prepared are characterized by using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), Brunauer-Emmett-Teller (BET) surface area analysis, and X-ray photoelectron spectroscopy (XPS). Photocatalysts explored have particle sizes >= 50 nm. This is deliberately done in order to avoid the nanotoxic size regime of ZnO. Despite the large particle size and low specific surface area (<20 m(2).g(-1)), the best catalyst reported here compare favorably with recent reports on ZnO based systems. Using X-photoelectron spectroscopy and synthesis property correlations, we infer that the presence of multivalent Cu (most likely in the form of Cu1+delta) on ZnO surface is responsible for the observed photoactivity enhancement.

Scaling of pressure spectrum in turbulent boundary layers

Scaling of pressure spectrum in zero-pressure-gradient turbulent boundary layers is discussed. Spatial DNS data of boundary layer at one time instant (Re-theta = 4500) are used for the analysis. It is observed that in the outer regions the pressure spectra tends towards the -7/3 law predicted by Kolmogorov's theory of small-scale turbulence. The slope in the pressure spectra varies from -1 close to the wall to a value close to -7/3 in the outer region. The streamwise velocity spectra also show a -5/3 trend in the outer region of the flow. The exercise carried out to study the amplitude modulation effect of the large scales on the smaller ones in the near-wall region reveals a strong modulation effect for the streamwise velocity, but not for the pressure fluctuations. The skewness of the pressure follows the same trend as the amplitude modulation coefficient, as is the case for the velocity. In the inner region, pressure spectra were seen to collapse better when normalized with the local Reynolds stress (-(u'v') over bar) than when scaled with the local turbulent kinetic energy (q(2) = (u'(2)) over bar + (v'(2)) over bar + (w'(2)) over bar)

A VARIABLE SWITCHING FREQUENCY PWM TECHNIQUE FOR INVERTER-FED INDUCTION MOTOR TO ACHIEVE SPREAD SPECTRUM

Voltage Source Inverter (VSI) fed induction motors are widely used in variable speed applications. For inverters using fixed switching frequency PWM, the output harmonic spectra are located at a few discrete frequencies. The ac motordrives powered by these inverters cause acoustic noise. This paper proposes a new variable switching frequency pwm technique and compares its performance with constant switching frequency pwm technique. It is shown that the proposed technique leads to spread spectra of voltages and currents. Also this technique ensures that no lower order harmonics are present and the current THD is comparable to that of fixed switching frequency PWM and is even better for higher modulation indices.

Fourier spectrum based extraction of an equivalent trap state density in indium gallium zinc oxide transistors

Segregating the dynamics of gate bias induced threshold voltage shift, and in particular, charge trapping in thin film transistors (TFTs) based on time constants provides insight into the different mechanisms underlying TFTs instability. In this Letter we develop a representation of the time constants and model the magnitude of charge trapped in the form of an equivalent density of created trap states. This representation is extracted from the Fourier spectrum of the dynamics of charge trapping. Using amorphous In-Ga-Zn-O TFTs as an example, the charge trapping was modeled within an energy range of Delta E-t approximate to 0.3 eV and with a density of state distribution as D-t(Et-j) = D-t0 exp(-Delta E-t/kT) with D-t0 = 5.02 x 10(11) cm(-2) eV(-1). Such a model is useful for developing simulation tools for circuit design. (C) 2014 AIP Publishing LLC.

Propensity to Form Amyloid Fibrils Is Encoded as Excitations in the Free Energy Landscape of Monomeric Proteins

Protein aggregation, linked to many of diseases, is initiated when monomers access rogue conformations that are poised to form amyloid fibrils. We show, using simulations of src SH3 domain, that mechanical force enhances the population of the aggregation-prone (N*) states, which are rarely populated under force free native conditions but are encoded in the spectrum of native fluctuations. The folding phase diagrams of SH3 as a function of denaturant concentration (C]), mechanical force (f), and temperature exhibit an apparent two-state behavior, without revealing the presence of the elusive N* states. Interestingly, the phase boundaries separating the folded and unfolded states at all C] and f fall on a master curve, which can be quantitatively described using an analogy to superconductors in a magnetic field. The free energy profiles as a function of the molecular extension (R), which are accessible in pulling experiments, (R), reveal the presence of a native-like N* with a disordered solvent-exposed amino-terminal beta-strand. The structure of the N* state is identical with that found in Fyn SH3 by NMR dispersion experiments. We show that the timescale for fibril formation can be estimated from the population of the N* state, determined by the free energy gap separating the native structure and the N* state, a finding that can be used to assess fibril forming tendencies of proteins. The structures of the N* state are used to show that oligomer formation and likely route to fibrils occur by a domain-swap mechanism in SH3 domain. (C) 2014 Elsevier Ltd. All rights reserved.

Fine-Tuning Dual Emission and Aggregation-Induced Emission Switching in NPI-BODIPY Dyads

Three new NPI-BODIPY dyads 1-3 (NPI = 1,8-naphthalimide, BODIPY = boron-dipyrromethene) were synthesized, characterized, and studied. The NPI and BODIPY moieties in these dyads are electronically separated by oxoaryl bridges, and the compounds only differ structurally with respect to methyl substituents on the BODIPY fluorophore. The NPI and BODIPY moieties retain their optical features in molecular dyads 1-3. Dyads 1-3 show dual emission in solution originating from the two separate fluorescent units. The variations of the dual emission in these compounds are controlled by the structural flexibilities of the systems. Dyads 13, depending on their molecular flexibilities, show considerably different spectral shapes and dissimilar intensity ratios of the two emission bands. The dyads also show significant aggregation-induced emission switching (AIES) on formation of nano-aggregates in THF/H2O with changes in emission color from green to red. Whereas the flexible and aggregation-prone compound 1 shows AIES, rigid systems with less favorable intermolecular interactions (i.e., 2 and 3) show aggregation-induced quenching of emission. Correlations of the emission intensity and structural flexibility were found to be reversed in solution and aggregated states. Photophysical and structural investigations suggested that intermolecular interactions (e. g., pi-pi stacking) play a major role in controlling the emission of these compounds in the aggregated state.

Unusual eigenvalue spectrum and relaxation in the Levy-Ornstein-Uhlenbeck process

We consider the rates of relaxation of a particle in a harmonic well, subject to Levy noise characterized by its Levy index mu. Using the propagator for this Levy-Ornstein-Uhlenbeck process (LOUP), we show that the eigenvalue spectrum of the associated Fokker-Planck operator has the form (n + m mu)nu where nu is the force constant characterizing the well, and n, m is an element of N. If mu is irrational, the eigenvalues are all nondegenerate, but rational mu can lead to degeneracy. The maximum degeneracy is shown to be 2. The left eigenfunctions of the fractional Fokker-Planck operator are very simple while the right eigenfunctions may be obtained from the lowest eigenfunction by a combination of two different step-up operators. Further, we find that the acceptable eigenfunctions should have the asymptotic behavior vertical bar x vertical bar(-n1-n2 mu) as vertical bar x vertical bar -> infinity, with n(1) and n(2) being positive integers, though this condition alone is not enough to identify them uniquely. We also assert that the rates of relaxation of LOUP are determined by the eigenvalues of the associated fractional Fokker-Planck operator and do not depend on the initial state if the moments of the initial distribution are all finite. If the initial distribution has fat tails, for which the higher moments diverge, one can have nonspectral relaxation, as pointed out by Toenjes et al. Phys. Rev. Lett. 110, 150602 (2013)].

Spectrum sensing using distributed sequential detection via noisy reporting MAC

This paper considers cooperative spectrum sensing algorithms for Cognitive Radios which focus on reducing the number of samples to make a reliable detection. We propose algorithms based on decentralized sequential hypothesis testing in which the Cognitive Radios sequentially collect the observations, make local decisions and send them to the fusion center for further processing to make a final decision on spectrum usage. The reporting channel between the Cognitive Radios and the fusion center is assumed more realistically as a Multiple Access Channel (MAC) with receiver noise. Furthermore the communication for reporting is limited, thereby reducing the communication cost. We start with an algorithm where the fusion center uses an SPRT-like (Sequential Probability Ratio Test) procedure and theoretically analyze its performance. Asymptotically, its performance is close to the optimal centralized test without fusion center noise. We further modify this algorithm to improve its performance at practical operating points. Later we generalize these algorithms to handle uncertainties in SNR and fading. (C) 2014 Elsevier B.V. All rights reserved.

Spectrum of the three-dimensional fuzzy well

We develop the formalism of quantum mechanics on three-dimensional fuzzy space and solve the Schrodinger equation for the free particle, finite and infinite fuzzy wells. We show that all results reduce to the appropriate commutative limits. A high energy cut-off is found for the free particle spectrum, which also results in the modification of the high energy dispersion relation. An ultra-violet/infra-red duality is manifest in the free particle spectrum. The finite well also has an upper bound on the possible energy eigenvalues. The phase shifts due to scattering around the finite fuzzy potential well are calculated.

Group Testing-Based Spectrum Hole Search for Cognitive Radios

This paper investigates the use of adaptive group testing to find a spectrum hole of a specified bandwidth in a given wideband of interest. We propose a group testing-based spectrum hole search algorithm that exploits sparsity in the primary spectral occupancy by testing a group of adjacent subbands in a single test. This is enabled by a simple and easily implementable sub-Nyquist sampling scheme for signal acquisition by the cognitive radios (CRs). The sampling scheme deliberately introduces aliasing during signal acquisition, resulting in a signal that is the sum of signals from adjacent subbands. Energy-based hypothesis tests are used to provide an occupancy decision over the group of subbands, and this forms the basis of the proposed algorithm to find contiguous spectrum holes of a specified bandwidth. We extend this framework to a multistage sensing algorithm that can be employed in a variety of spectrum sensing scenarios, including noncontiguous spectrum hole search. Furthermore, we provide the analytical means to optimize the group tests with respect to the detection thresholds, number of samples, group size, and number of stages to minimize the detection delay under a given error probability constraint. Our analysis allows one to identify the sparsity and SNR regimes where group testing can lead to significantly lower detection delays compared with a conventional bin-by-bin energy detection scheme; the latter is, in fact, a special case of the group test when the group size is set to 1 bin. We validate our analytical results via Monte Carlo simulations.

Quick re-introduction of selective scalar interactions in a pure-shift NMR spectrum

A new 1D NMR experiment cited as `Quick G-SERF', which re-introduces selective proton-proton scalar interactions in a pure shift spectrum during real time data acquisition, is reported. The method provides information on multiple proton-proton couplings from a single experiment, analogous to the 2D G-SERF technique, while significantly shortening the experimental time by 1-2 orders of magnitude due to reduced dimension and enhanced sensitivity.

Assignment of the C-13 NMR spectrum by correlation to dipolar coupled proton-pairs and estimation of order parameters of a thiophene based liquid crystal

Materials with widely varying molecular topologies and exhibiting liquid crystalline properties have attracted considerable attention in recent years. C-13 NMR spectroscopy is a convenient method for studying such novel systems. In this approach the assignment of the spectrum is the first step which is a non-trivial problem. Towards this end, we propose here a method that enables the carbon skeleton of the different sub-units of the molecule to be traced unambiguously. The proposed method uses a heteronuclear correlation experiment to detect pairs of nearby carbons with attached protons in the liquid crystalline core through correlation of the carbon chemical shifts to the double-quantum coherences of protons generated through the dipolar coupling between them. Supplemented by experiments that identify non-protonated carbons, the method leads to a complete assignment of the spectrum. We initially apply this method for assigning the C-13 spectrum of the liquid crystal 4-n-pentyl-4'-cyanobiphenyl oriented in the magnetic field. We then utilize the method to assign the aromatic carbon signals of a thiophene based liquid crystal thereby enabling the local order-parameters of the molecule to be estimated and the mutual orientation of the different sub-units to be obtained.

Chaperone protein HYPK interacts with the first 17 amino acid region of Huntingtin and modulates mutant HTT-mediated aggregation and cytotoxicity

Huntington's disease is a polyglutamine expansion disorder, characterized by mutant HTT-mediated aggregate formation and cytotoxicity. Many reports suggests roles of N-terminal 17 amino acid domain of HTT (HTT-N17) towards subcellular localization, aggregate formation and subsequent pathogenicity induced by N-terminal HTT harboring polyQ stretch in pathogenic range. HYPK is a HTT-interacting chaperone which can reduce N-terminal mutant HTT-mediated aggregate formation and cytotoxicity in neuronal cell lines. However, how HYPK interacts with N-terminal fragment of HTT remained unknown. Here we report that specific interaction of HYPK with HTT-N17 is crucial for the chaperone activity of HYPK. Deletion of HTT-N17 leads to formation of tinier, SDS-soluble nuclear aggregates formed by N-terminal mutant HTT. The increased cytotoxicity imparted by these tiny aggregates might be contributed due to loss of interaction with HYPK. (C) 2014 Elsevier Inc. All rights reserved.

Suppression of protein aggregation by gold nanoparticles: a new way to store and transport proteins

Suppression of the aggregation of proteins has tremendous implications in biology and medicine. In the pharmaceuticals industry, aggregation of therapeutically important proteins and peptides while stored, reduces the efficacy and promptness of action leading to, in many instances, intoxication of the patient by the aggregate. Here we report the effect of gold nanoparticles (Au-NPs) in preventing the thermal and chemical aggregation of two unrelated proteins of different size, alcohol dehydrogenase (ADH, 84 kDa) and insulin (6 kDa), respectively, in physiological pH. Our principal observation is that there is a significant reduction (up to 95%) in the extent of aggregation of ADH and insulin in the presence of gold nanoparticles (Au-NPs). Aggregation of these proteins at micromolar concentration is prevented using nanomolar or less amounts of gold nanoparticles which is remarkable since chaperones which prevent such aggregation in vivo are required in micromolar quantity. The prevention of aggregation of these two different proteins under two different denaturing environments has established the role of Au-NPs as a protein aggregation prevention agent. The extent of prevention increases rapidly with the increase in the size of the gold nanoparticles. Protein molecules get physisorbed on the gold nanoparticle surface and thus become inaccessible by the denaturing agent in solution. This adsorption of proteins on AuNPs has been established by a variety of techniques and assays.