Al3+-Ion-Triggered Conformational Isomerization of a Rhodamine B Derivative Evidenced by a Fluorescence Signal - A Crystallographic Proof

A newly designed rhodamine B anisaldehyde hydrazone exhibits Al3+-ion-induced cis (L) to trans (L) conformational isomerization with respect to the xanthene moiety through a rotation about a N-N bond; the isomerization is indicated by a detectable naked-eye color change and a turn-on red fluorescence in 4-(2-hydroxyethyl)-1-piperazineethanesulfonic acid (HEPES) buffer (EtOH/Water 1:9 v/v; pH 7.4) at 25 degrees C. In support of this observation, detailed spectroscopic and physicochemical studies along with density function theory (DFT) calculations have been performed. This cis-to-trans conformational isomerization is due to Al3+ ion coordination, which induces this visual color change and the turn-on fluorescence response. To strengthen our knowledge of the conformational isomerization, detailed structural characterizations of the cis and trans isomers in the solid state were performed by single-crystal X-ray diffraction. To the best of our knowledge, this is the first structural report of both cis and trans conformational isomers for this family of compounds. Moreover, this noncytotoxic probe could be used to image the accumulation of Al3+ ions in HeLa and MCF-7 cell lines.

A provably tight delay-driven concurrently congestion mitigating global routing algorithm

Routing is a very important step in VLSI physical design. A set of nets are routed under delay and resource constraints in multi-net global routing. In this paper a delay-driven congestion-aware global routing algorithm is developed, which is a heuristic based method to solve a multi-objective NP-hard optimization problem. The proposed delay-driven Steiner tree construction method is of O(n(2) log n) complexity, where n is the number of terminal points and it provides n-approximation solution of the critical time minimization problem for a certain class of grid graphs. The existing timing-driven method (Hu and Sapatnekar, 2002) has a complexity O(n(4)) and is implemented on nets with small number of sinks. Next we propose a FPTAS Gradient algorithm for minimizing the total overflow. This is a concurrent approach considering all the nets simultaneously contrary to the existing approaches of sequential rip-up and reroute. The algorithms are implemented on ISPD98 derived benchmarks and the drastic reduction of overflow is observed. (C) 2014 Elsevier Inc. All rights reserved.

Influence of initial degree of saturation on swell pressures of compacted Barmer bentonite specimens

Densely compacted bentonite or bentonite-sand mixture has been identified as suitable buffer in deep geological repositories as its exceptionally high swelling capacity enables tight contact between the waste canister and surrounding rock. The degree of saturation of the compacted bentonite buffer can increase upon ingress of groundwater from the surrounding rock mass or decrease from evaporation due to high temperature (50-210 degrees C) derived from the waste canister. Available studies indicate that the influence of initial moisture content or degree of saturation on the swell pressure or swell potential of compacted bentonites is unclear. Some studies suggest that initial degree of saturation has an influence, while others suggest that it does not have bearing on the swell pressure of compacted bentonites. This paper examines the influence of initial degree of saturation in montmorillonite voids (termed,S-r,S-MF) on swell pressure of compacted Barmer bentonite-sand mixtures (dry density range: 1.4-2 Mg/m(3)) from micro-structural considerations. The experimental results bring out that, constant dry density specimens that developed similar number of hydration layers upon wetting developed comparable swell pressures and were unaffected by variations in initial S-r,S-MF values. Comparatively, constant dry density specimens that developed dis-similar number of hydration layers upon wetting established different swell pressures and were responsive to variations in initial S-r,S-MF. (C) 2015 Elsevier Ltd. All rights reserved.

Synthesis of cadmium oxide and carbon nanotube based nanocomposites and their use as a sensing interface for xanthine detection

Xanthine oxidase (XOD) extracted from bovine milk was immobilized covalently via N-ethyl-N'-(3-dimethylaminopropyl) carbodiimide (EDC) and N-hydroxy succinimide (NHS) chemistry onto cadmium oxide nanoparticles (CdO)/carboxylated multiwalled carbon nanotube (c-MWCNT) composite film electrodeposited on the surface of an Au electrode. The nanocomposite modified Au electrode was characterized by Fourier transform infrared (FTIR), cyclic voltammetry (CV), scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS) before and after immobilization of XOD. Under optimal operation conditions (25 degrees C, + 0.2 V vs. Ag/AgCl, sodium phosphate buffer, pH 7.5), the following characteristics are attributed to the biosensor: linearity of response up to xanthine concentrations of 120 mu M, detection limit of 0.05 mu M (S/N = 3) and a response time of at most 4 s. After being used 100 times over a period of 120 days, only 50% loss of the initial activity of the biosensor was evaluated when stored at 4 degrees C. The fabricated biosensor was successfully employed for the determination of xanthine in fish meat.

A rhodamine-based `turn-on' Al3+ ion-selective reporter and the resultant complex as a secondary sensor for F- ion are applicable to living cell staining

A newly designed fluorescent aluminum(III) complex (L'-Al; 2) of a structurally characterized non-fluorescent rhodamine Schiff base (L) has been isolated in pure form and characterized using spectroscopic and physico-chemical methods with theoretical density functional theory (DFT) support. On addition of Al(III) ions to a solution of L in HEPES buffer (1 mM, pH 7.4; EtOH-water, 1 : 3 v/v) at 25 degrees C, the systematic increase in chelation-enhanced fluorescence (CHEF) enables the detection of Al(III) ions as low as 60 nM with high selectivity, unaffected by the presence of competitive ions. Interestingly, the Al(III) complex (L'-Al; 2) is specifically able to detect fluoride ions by quenching the fluorescence in the presence of large amounts of other anions in the HEPES buffer (1 mM, pH 7.4) at 25 degrees C. On the basis of our experimental and theoretical findings, the addition of Al3+ ions to a solution of L helps to generate a new fluorescence peak at 590 nm, due to the selective binding of Al3+ ions with L in a 1 : 1 ratio with a binding constant (K) of 8.13 x 10(4) M-1. The Schiff base L shows no cytotoxic effect, and it can therefore be employed for determining the intracellular concentration of Al3+ and F-ions by 2 in living cells using fluorescence microscopy.

Cocrystals of Hydrochlorothiazide: Solubility and Diffusion/Permeability Enhancements through Drug-Coformer Interactions

Hydrochlorothiazide (HCT) is a diuretic and a BCS class IV drug with low solubility and low permeability, exhibiting poor oral absorption. The present study attempts to improve the physicochemical properties of the drug using a crystal engineering approach with cocrystals. Such multicomponent crystals of HCT with nicotinic acid (NIC), nicotinamide (NCT), 4-aminobenzoic acid (PABA), succinamide (SAM), and resorcinol (RES) were prepared using liquid-assisted grinding, and their solubilities in pH 7.4 buffer were evaluated. Diffusion and membrane permeability were studied using a Franz diffusion cell. Except for the SAM and NIC cocrystals, all other binary systems exhibited improved solubility. All of the cocrystals showed improved diffusion/membrane permeability compared to that of HCT with the exception of the SAM cocrystal. When the solubility was high, as in the case of PABA, NCT, and RES cocrystals, the flux/permeability dropped slightly. This is in agreement with the expected interplay between solubility and permeability. Improved solubility/permeability is attributed to new drug-coformer interactions. Cocrystals of SAM, however, showed poor solubility and flux This cocrystal contains a primary sulfonamide dimer synthon similar to that of HCT polymorphs, which may be a reason for its unusual behavior. Hirshfeld surface analysis was carried out in all cases to determine whether a correlation exists between cocrystal permeability and drug-coformer interactions.

Energy Sharing for Multiple Sensor Nodes With Finite Buffers

We consider the problem of finding optimal energy sharing policies that maximize the network performance of a system comprising of multiple sensor nodes and a single energy harvesting (EH) source. Sensor nodes periodically sense the random field and generate data, which is stored in the corresponding data queues. The EH source harnesses energy from ambient energy sources and the generated energy is stored in an energy buffer. Sensor nodes receive energy for data transmission from the EH source. The EH source has to efficiently share the stored energy among the nodes to minimize the long-run average delay in data transmission. We formulate the problem of energy sharing between the nodes in the framework of average cost infinite-horizon Markov decision processes (MDPs). We develop efficient energy sharing algorithms, namely Q-learning algorithm with exploration mechanisms based on the epsilon-greedy method as well as upper confidence bound (UCB). We extend these algorithms by incorporating state and action space aggregation to tackle state-action space explosion in the MDP. We also develop a cross entropy based method that incorporates policy parameterization to find near optimal energy sharing policies. Through simulations, we show that our algorithms yield energy sharing policies that outperform the heuristic greedy method.

BODIPY appended copper(II) complexes of curcumin showing mitochondria targeted remarkable photocytotoxicity in visible light

Copper(II) complexes of BODIPY (borondipyrromethene) derivatives (L-1, L-2) and curcumin (Hcur), viz. Cu(L-1)(cur)]Cl (1) and Cu(L-2)(cur)]Cl (2), where L-1 and L-2 are the non-iodinated and diiodinated BODIPY appended dipicolylamine ligands, are prepared and characterized and their photocytotoxic activity in visible light studied. Binding to copper(II) has rendered stability to curcumin from its hydrolytic degradation in buffer medium. The complexes show mitochondrial localization in HeLa cells emphasizing the findings that both 1 and 2 are mitochondria-targeting complexes and induce cancer cell death. Complex 1 with a fluorophoric BODIPY moiety in L-1 gave IC50 values of 7.9(+/- 0.3) mu M in visible light (400-700 nm) and 29.1(+/- 0.5) mu M in the dark. Complex 2 having a diiodo BODIPY moiety in L-2 as a photosensitizer gave IC50 values of 3.8(+/- 0.2) mu M in visible light and 32.1(+/- 0.4) mu M in the dark. The PDT effect of 2 is comparable to that of Photofrin (R), an FDA approved PDT drug. Cell death follows an apoptotic pathway with the formation of reactive oxygen species (ROS).

Simultaneous Determination of Catecholamines in Presence of Uric Acid and Ascorbic Acid at a Highly Sensitive Electrochemically Activated Carbon Paste Electrode

A simple yet remarkable, electrochemically activated carbon paste electrode (EACPE) was prepared by successive potential cycling of carbon paste in a 0.1 M NaOH solution and was effectively used for the simultaneous determination of catecholamines such as dopamine (DA), epinephrine (E) and Norepinephrine (NE) in presence of uric acid (UA) and ascorbic acid (AA). Taking DA as the ideal catecholamine, the electrochemical behaviors of DA, UA and AA such as scan rate and pH variation was studied by cyclic voltammetry (CV) in phosphate buffer solution (PBS, pH 7.1). This electrochemical sensor exhibited strong electrocatalytic activity towards the oxidation of a mixture of catecholamines, UA and AA with apparent reduction of overpotentials. Crider optimum conditions, limit of detection (S/N = 3) of DA, E, NE, UA and AA was found to be 0.08, 0.08, 0.07, 0.1 and 6.0 mu M, respectively by differential pulse voltammetry (DPV). The analytical performance of this modified electrode as a biosensor was also demonstrated for the determination of DA, UA and AA in dopamine injection, human urine and vitamin C tablets, respectively, in presence of other interfering substances. (C) 2015 The Electrochemical Society. All-rights reserved.

Wireless scheduling with partial channel state information: large deviations and optimality

We consider a server serving a time-slotted queued system of multiple packet-based flows, where not more than one flow can be serviced in a single time slot. The flows have exogenous packet arrivals and time-varying service rates. At each time, the server can observe instantaneous service rates for only a subset of flows ( selected from a fixed collection of observable subsets) before scheduling a flow in the subset for service. We are interested in queue length aware scheduling to keep the queues short. The limited availability of instantaneous service rate information requires the scheduler to make a careful choice of which subset of service rates to sample. We develop scheduling algorithms that use only partial service rate information from subsets of channels, and that minimize the likelihood of queue overflow in the system. Specifically, we present a new joint subset-sampling and scheduling algorithm called Max-Exp that uses only the current queue lengths to pick a subset of flows, and subsequently schedules a flow using the Exponential rule. When the collection of observable subsets is disjoint, we show that Max-Exp achieves the best exponential decay rate, among all scheduling algorithms that base their decision on the current ( or any finite past history of) system state, of the tail of the longest queue. To accomplish this, we employ novel analytical techniques for studying the performance of scheduling algorithms using partial state, which may be of independent interest. These include new sample-path large deviations results for processes obtained by non-random, predictable sampling of sequences of independent and identically distributed random variables. A consequence of these results is that scheduling with partial state information yields a rate function significantly different from scheduling with full channel information. In the special case when the observable subsets are singleton flows, i.e., when there is effectively no a priori channel state information, Max-Exp reduces to simply serving the flow with the longest queue; thus, our results show that to always serve the longest queue in the absence of any channel state information is large deviations optimal.

Trap modulated photoresponse of InGaN/Si isotype heterojunction at zero-bias

n-n isotype heterojunction of InGaN and bare Si (111) was formed by plasma assisted molecular beam epitaxy without nitridation steps or buffer layers. High resolution X-ray diffraction studies were carried out to confirm the formation of epilayers on Si (111). X-ray rocking curves revealed the presence of large number of edge threading dislocations at the interface. Room temperature photoluminescence studies were carried out to confirm the bandgap and the presence of defects. Temperature dependent I-V measurements of Al/InGaN/Si (111)/Al taken in dark confirm the rectifying nature of the device. I-V characteristics under UV illumination, showed modest rectification and was operated at zero bias making it a self-powered device. A band diagram of the heterojunction is proposed to understand the transport mechanism for self-powered functioning of the device. (c) 2015 AIP Publishing LLC.

High Catalytic Activity of Amorphous Ir-Pi for Oxygen Evolution Reaction

Large-scale production of hydrogen gas by water electrolysis is hindered by the sluggish kinetics of oxygen evolution reaction (OER) at the anode. The development of a highly active and stable catalyst for OER is a challenging task. Electrochemically prepared amorphous metal-based catalysts have gained wide attention after the recent discovery of a cnbalt-phosphate (Co-Pi) catalyst: Herein, an amorphous iridium-phosphate (Ir-Pi) is investigated as an oxygen evolution catalyst. The catalyst is prepared by the anodic polarization of carbon paper electrodes in neutral phosphate buffer solutions containing IrCl3. The Ir-Pi film deposited on the substrate has significant amounts of phosphate and It centers in an oxidation state higher than +4. Phosphate plays a significant role in the deposition of the catalyst and also in its activity toward OER. The onset potential of OER on the Ir-Pi is about 150 mV lower in comparison with the Co-Pi under identical experimental conditions. Thus, Ir-Pi is a promising catalyst for electrochemical oxidation of water.

Performance of New Dynamic Benefit-Weighted Scheduling Scheme in DiffServ Networks

In this paper, we design a new dynamic packet scheduling scheme suitable for differentiated service (DiffServ) network. Designed dynamic benefit weighted scheduling (DBWS) uses a dynamic weighted computation scheme loosely based on weighted round robin (WRR) policy. It predicts the weight required by expedited forwarding (EF) service for the current time slot (t) based on two criteria; (i) previous weight allocated to it at time (t-1), and (ii) the average increase in the queue length of EF buffer. This prediction provides smooth bandwidth allocation to all the services by avoiding overbooking of resources for EF service and still providing guaranteed services for it. The performance is analyzed for various scenarios at high, medium and low traffic conditions. The results show that packet loss is minimized, end to end delay is minimized and jitter is reduced and therefore meet quality of service (QoS) requirement of a network.

Estimation of background carrier concentration in fully depleted GaN films

Buffer leakage is an important parasitic loss mechanism in AlGaN/GaN high electron mobility transistors (HEMTs) and hence various methods are employed to grow semi-insulating buffer layers. Quantification of carrier concentration in such buffers using conventional capacitance based profiling techniques is challenging due to their fully depleted nature even at zero bias voltages. We provide a simple and effective model to extract carrier concentrations in fully depleted GaN films using capacitance-voltage (C-V) measurements. Extensive mercury probe C-V profiling has been performed on GaN films of differing thicknesses and doping levels in order to validate this model. Carrier concentrations as extracted from both the conventional C-V technique for partially depleted films having the same doping concentration, and Hall measurements show excellent agreement with those predicted by the proposed model thus establishing the utility of this technique. This model can be readily extended to estimate background carrier concentrations from the depletion region capacitances of HEMT structures and fully depleted films of any class of semiconductor materials.

Amperometric acetylcholinesterase biosensor for pesticides monitoring utilising iron oxide nanoparticles and poly(indole-5-carboxylic acid)

A new electrochemical sensing device was constructed for determination of pesticides. In this report, acetylcholinesterase was bioconjugated onto hybrid nanocomposite, i.e. iron oxide nanoparticles and poly(indole-5-carboxylic acid) (Fe(3)O(4)NPs/Pin5COOH) was deposited electrochemically on glassy carbon electrode. Fe(3)O(4)NPs was showed as an amplified sensing interface at lower voltage which makes the sensor more sensitive and specific. The enzyme inhibition by pesticides was detected within concentrations ranges between 0.1-60 and 1.5-70 nM for malathion and chlorpyrifos, respectively, under optimal experimental conditions (sodium phosphate buffer, pH 7.0 and 25 degrees C). Biosensor determined the pesticides level in water samples (spiked) with satisfactory accuracy (96%-100%). Sensor showed good storage stability and retained 50% of its initial activity within 70 days at 4 degrees C.