Iron(III) Schiff base complexes of arginine and lysine as netropsin mimics showing AT-selective DNA binding and photonuclease activity

Iron(III) complexes [Fe(L)(2)]Cl (1-3), where L is monoanionic N-salicylidene-arginine (sal-argH for 1), hydroxynaphthylidene-arginine (nap-argH for 2) and N-salicylidene-lysine (sal-lysH for 3), were prepared and their DNA binding and photo-induced DNA cleavage activity studied. Complex 3 as its hexafluorophosphate salt [Fe(sal-lysH)(2)](PF6)center dot 6H(2)O (3a) was structurally characterized by single crystal Xray crystallography. The crystals belonged to the triclinic space group P-1. The complex has two tridentate ligands in FeN2O4 coordination geometry with two pendant cationic amine moieties. Complexes 1 and 2 with two pendant cationic guanidinium moieties are the structural models for the antitumor antibiotics netropsin. The complexes are stable and soluble in water. They showed quasi-reversible Fe(III)/Fe(II) redox couple near 0.6 V in H2O-0.1 M KCl. The high-spin 3d(5)-iron(III) complexes with mu(eff) value of similar to 5.9 mu(B) displayed ligand-to-metal charge transfer electronic band near 500 mm in Tris-HCl buffer. The complexes show binding to Calf Thymus (CT) DNA. Complex 2 showed better binding propensity to the synthetic oligomer poly(dA)center dot poly(dT) than to CT-DNA or poly(dG)center dot poly(dC). All the complexes displayed chemical nuclease activity in the presence of 3-mercaptopropionic acid as a reducing agent and cleaved supercoiled pUC19 DNA to its nicked circular form. They exhibited photo-induced DNA cleavage activity in UV-A light and visible light via a mechanistic pathway that involves the formation of reactive hydroxyl radical species. (C) 2010 Elsevier Inc. All rights reserved.

Detection of multicode STBC signals in frequency selective fading

Multicode operation in space-time block coded (STBC) multiple input multiple output (MIMO) systems can provide additional degrees of freedom in code domain to achieve high data rates. In such multicode STBC systems, the receiver experiences code domain interference (CDI) in frequency selective fading. In this paper, we propose a linear parallel interference cancellation (LPIC) approach to cancel the CDI in multicode STBC in frequency selective fading. The proposed detector first performs LPIC followed by STBC decoding. We evaluate the bit error performance of the detector and show that it effectively cancels the CDI and achieves improved error performance. Our results further illustrate how the combined effect of interference cancellation, transmit diversity, and RAKE diversity affect the bit error performance of the system.

On the maximal rate of non-square STBCs from complex orthogonal designs

A Linear Processing Complex Orthogonal Design (LPCOD) is a p x n matrix epsilon, (p >= n) in k complex indeterminates x(1), x(2),..., x(k) such that (i) the entries of epsilon are complex linear combinations of 0, +/- x(i), i = 1,..., k and their conjugates, (ii) epsilon(H)epsilon = D, where epsilon(H) is the Hermitian (conjugate transpose) of epsilon and D is a diagonal matrix with the (i, i)-th diagonal element of the form l(1)((i))vertical bar x(1)vertical bar(2) + l(2)((i))vertical bar x(2)vertical bar(2)+...+ l(k)((i))vertical bar x(k)vertical bar(2) where l(j)((i)), i = 1, 2,..., n, j = 1, 2,...,k are strictly positive real numbers and the condition l(1)((i)) = l(2)((i)) = ... = l(k)((i)), called the equal-weights condition, holds for all values of i. For square designs it is known. that whenever a LPCOD exists without the equal-weights condition satisfied then there exists another LPCOD with identical parameters with l(1)((i)) = l(2)((i)) = ... = l(k)((i)) = 1. This implies that the maximum possible rate for square LPCODs without the equal-weights condition is the same as that or square LPCODs with equal-weights condition. In this paper, this result is extended to a subclass of non-square LPCODs. It is shown that, a set of sufficient conditions is identified such that whenever a non-square (p > n) LPCOD satisfies these sufficient conditions and do not satisfy the equal-weights condition, then there exists another LPCOD with the same parameters n, k and p in the same complex indeterminates with l(1)((i)) = l(2)((i)) = ... = l(k)((i)) = 1.

Solution of MDPS using simulation-based value iteration

This article proposes a three-timescale simulation based algorithm for solution of infinite horizon Markov Decision Processes (MDPs). We assume a finite state space and discounted cost criterion and adopt the value iteration approach. An approximation of the Dynamic Programming operator T is applied to the value function iterates. This 'approximate' operator is implemented using three timescales, the slowest of which updates the value function iterates. On the middle timescale we perform a gradient search over the feasible action set of each state using Simultaneous Perturbation Stochastic Approximation (SPSA) gradient estimates, thus finding the minimizing action in T. On the fastest timescale, the 'critic' estimates, over which the gradient search is performed, are obtained. A sketch of convergence explaining the dynamics of the algorithm using associated ODEs is also presented. Numerical experiments on rate based flow control on a bottleneck node using a continuous-time queueing model are performed using the proposed algorithm. The results obtained are verified against classical value iteration where the feasible set is suitably discretized. Over such a discretized setting, a variant of the algorithm of [12] is compared and the proposed algorithm is found to converge faster.

Photocytotoxic Lanthanum(III) and Gadolinium(III) Complexes of Phenanthroline Bases Showing Light-Induced DNA Cleavage Activity

Lanthanide complexes of formulation [La(B)(2)(NO3)(3)] (1-3) and [Gd(B)(2)(NO3)(3)] (4-6), where B is a N,N-donor phenanthroline base, namely, 1,10-phenanthroline (phen in 1, 4),dipyrido[3,2-d2',3'-f]quinoxaline (dpq in 2,5) and dipyrido[3,2-a2',3'-c]phenazine (dppz in 3, 6), have been prepared, characterized from physicochemical data, and their photoinduced DNA and protein cleavage activity studied The photocytotoxicity of the dppz complexes 3 and 6 has been studied using HeLa cancer cells. The complexes exhibitligand centered bands in the UV region The dppz complexes show thelowest energy band at 380 nm in N,N-dimethylformamide (DMF) The La(III)complexes are diamagnetic. The Gd(III) complexes (4-6) have magneticmoments that correspond to seven unpaired electrons The complexes are1(.)1 electrolytic in aqueous DMF The dpq and dppz complexes in DMFshow ligand-based reductions. The complexes display moderate binding propensity to calf thymus DNA giving binding constant values in the range of 5.7 x 10(4)-5.8 x 10(5) M-1 with a relative order. 3, 6 (dppz)> 2, 5 (dpq) > 1, 4 (phen) The binding data suggest DNA surface and/or groove binding nature of the complexes. The complexes do not show any hydrolytic cleavage of plasmid supercoiled pUC19 DNA. The dpq and dppz complexes efficiently cleave SC DNA to its nicked circular form onexposure to UV-A light of 365 nm at nanomolar complex concentration. Mechanistic studies reveal the involvement of singlet oxygen (O-1(2)) and hydroxyl radical (HO center dot) as the cleavage active species.The complexes show binding propensity to bovine serum albumin (BSA)protein giving K-BSA values of similar to 10(5) M-1. The dppz complexes 3 and 6 show BSA protein cleavage activity in UV-A light of 365 nm The dppz complexes 3 and 6 exhibit significant photocytotoxicity in HeLa cells giving respective IC50 values of 341 nM and 573 nM in UV-A light of 365 nm for an exposure time of 15 min (IC50 > 100 mu M in dark for both the complexes) Control experiments show significant dark and phototoxicity of the dppz base alone (IC50 = 413 nM in light with 4 h incubation in dark and 116 mu M in dark with 24 h incubation). A significant decrease in the dark toxicity of the dppz base is observedon binding to the lanthanide ions while retaining similar phototoxicity.

Role of silicon carbide/mercury interface in ignitrons

A new model of ignition in an ignitron, based on the electrical breakdown of the junction between the ignitor (semiconductor) and the mercury (metal) is proposed. A method of evaluating some of the ignition characteristics is also developed. The paper gives a critical summary of the various characteristics of the ignition process. The new model is stated and used to explain all the ignition characteristics. The experiments conducted in support of the various aspects of this model are also given.

Synthesis of Unnatural Selenocystines and beta-Aminodiselenides via Regioselective Ring-Opening of Sulfamidates Using a Sequential, One-Pot, Multistep Strategy

A variety of N-alkyl-beta-aminodiselenides have been synthesized in high yield from sulfamidates under mild reaction conditions using potassium selenocyanate and benzyltriethylammonium tetrathiomolybdate ([BnNEt3](2)MoS4) in a sequential, one-pot, multistep reaction. The tolerance of multifarious protecting groups under the reaction conditions is discussed. The methodology was successfully extended to the synthesis of selenocystine,3,3'-dialkylselenocystine, and 3,3'-diphenylisoselenocystine and their direct incorporation into peptides.

Investigations of a two-stage pulse tube cryocooler operating down to 2.5K

A two-stage pulse tube cryocooler (PTC) which produces a no-load temperature of similar to 2.5 K in its second stage at an operating frequency of 1.6 Hz has been designed and fabricated. The second stage of the system provides a refrigeration power of similar to 250 mW at 5.0 K. The system uses stainless steel meshes (mesh size 200) along with lead (Pb) granules and combinations of Pb, Er3Ni, and HoCu2 as the first and second stage regenerator materials, respectively. Experimental studies have been carried out on different pulse tube configurations by varying the dimensions of the pulse tubes and regenerators to arrive at the best one, which leads to the lowest no-load second stage cold head temperature. Using this configuration, detailed experimental studies have been conducted by varying the volume percentage ratios of the second stage regenerator materials such as HoCu2, Er3Ni, and Pb (with an average grain size of similar to 250 mu m). This article presents the results of our experimental studies on cryocoolers with the regenerator material arranged in layered structures. Comparative studies have also been presented for specific cases where the regenerator materials are arranged as a homogeneous mixture in the second stage. The experimental results clearly indicate that the design of PTCs should use only layered structures of regenerator materials and not homogenous mixtures.

Synthesis and Densification of Monolithic Zirconium Carbide by Reactive Hot Pressing

Synthesis and densification of monolithic zirconium carbide (ZrC) has been carried out by reactive hot pressing of zirconium (Zr) and graphite (C) powders in the molar ratios 1:1, 1.25:1, 1.5:1, and 2:1 at 40 MPa, 1200 degrees-1600 degrees C. Monolithic ZrC could be synthesized with a C/Zr ratio similar to 0.5-1.0 and the post heat-treated samples have the lattice parameter in the range 4.665 to 4.698 A. Densification improves with an increasing deviation from the stoichiometry. Fine-grained (similar to 1 mu m) and nearly fully dense material (99% RD) could be obtained at a temperature as low as 1200 degrees C with C/Zr similar to 0.67. Microstructural and XRD observations suggest that densification occurred at low temperatures with nonstoichiometric Zr-C powder mixtures.

Low-Complexity Near-ML Decoding of Large Non-Orthogonal STBCs using Reactive Tabu Search

Non-orthogonal space-time block codes (STBC) with large dimensions are attractive because they can simultaneously achieve both high spectral efficiencies (same spectral efficiency as in V-BLAST for a given number of transmit antennas) as well as full transmit diversity. Decoding of non-orthogonal STBCs with large dimensions has been a challenge. In this paper, we present a reactive tabu search (RTS) based algorithm for decoding non-orthogonal STBCs from cyclic division algebras (CDA) having largedimensions. Under i.i.d fading and perfect channel state information at the receiver (CSIR), our simulation results show that RTS based decoding of 12 X 12 STBC from CDA and 4-QAM with 288 real dimensions achieves i) 10(-3) uncoded BER at an SNR of just 0.5 dB away from SISO AWGN performance, and ii) a coded BER performance close to within about 5 dB of the theoretical MIMO capacity, using rate-3/4 turbo code at a spectral efficiency of 18 bps/Hz. RTS is shown to achieve near SISO AWGN performance with less number of dimensions than with LAS algorithm (which we reported recently) at some extra complexity than LAS. We also report good BER performance of RTS when i.i.d fading and perfect CSIR assumptions are relaxed by considering a spatially correlated MIMO channel model, and by using a training based iterative RTS decoding/channel estimation scheme.

Low-Complexity Near-MAP Decoding of Large Non-Orthogonal STBCs Using PDA

Non-orthogonal space-time block codes (STBC) from cyclic division algebras (CDA) are attractive because they can simultaneously achieve both high spectral efficiencies (same spectral efficiency as in V-BLAST for a given number of transmit antennas) as well as full transmit diversity. Decoding of non-orthogonal STBCs with hundreds of dimensions has been a challenge. In this paper, we present a probabilistic data association (PDA) based algorithm for decoding non-orthogonal STBCs with large dimensions. Our simulation results show that the proposed PDA-based algorithm achieves near SISO AWGN uncoded BER as well as near-capacity coded BER (within 5 dB of the theoretical capacity) for large non-orthogonal STBCs from CDA. We study the effect of spatial correlation on the BER, and show that the performance loss due to spatial correlation can be alleviated by providing more receive spatial dimensions. We report good BER performance when a training-based iterative decoding/channel estimation is used (instead of assuming perfect channel knowledge) in channels with large coherence times. A comparison of the performances of the PDA algorithm and the likelihood ascent search (LAS) algorithm (reported in our recent work) is also presented.

Adsorption of oxygen and reactivity with HCl on a barium-doped lead surface

X.p.s. studies on the adsorption of oxygen on a barium-covered Pb surface have shown the presence of two distinct types of oxygen species: oxidic, O2–, and the peroxo-like O2–2(ads), and the surface has been identified as a composite of PbO and BaPbO3. On a barium pre-covered surface, the sticking probability of oxygen on Pb is increased. The O2–(ads) species preferentially reacts with HCl forming PbCl2(ads)via proton abstraction, whereas O2–2(ads) is not reactive with HCl vapour. On the Pb surface, the PbCl2 overlayer reacts with excess HCl, forming a volatile compound believed to be Pb(ClHCl)2, while in the presence of coadsorbed barium, the stability of PbCl2 is increased and the activation energy for the reaction: PbCl2(ads)+ 2HCl(g) Pb(ClHCl)2(g) is increased. Stronger intermetallic interaction is suggested to be the reason for higher PbCl2 stability.

A rationalisation of fatigue thresholds in pearlitic steels using a theoretical model

From a detailed re-examination of results in the literature, the effects of microstructure sizes, namely interlamellar spacing, pearlitic colony size and the prior austentitic grain size on the thresholds for fatigue crack growth (ΔKth) and crack closure (Kcl, th) have been illustrated. It is shown that while interlamellar spacing explicitly controls yield strength, a similar effect on ΔKth cannot be expected. On the other hand, the pearlitic colony size is shown to strongly influence ΔKth and Kcl, th through the deflection and retardation of cracks at colony boundaries. Consequently, an increase in ΔKth and Kcl, th with colony size has been found. The development of a theoretical model to illustrate the effects of colony size, shear flow stress in the slip band and macroscopic yield strength on Kcl, th and ΔKth is presented. the model assumes colony boundaries as potential sites for slip band pile-up formation and subsequent crack deflection finally leading to zig-zag crack growth. Using the concepts of roughness induced crack closure, the magnitude of Kcl, th is quantified as a function of colony size. In deriving the model, the flow stress in the slip band has been considered to represent the work hardened state in pearlite. Comparison of the theoretically predicted trend with the experimental data demonstrates very good agreement. Further, the intrinsic or closure free component of the fatigue threshold, ΔKeff, th is found to be insensitive to colony size and interlamellar spacing. Using a criterion for intrinsic fatigue threshold which considers the attainment of a critical fracture stress over a characteristic distance corresponding to interlamellar spacing, ΔKth values at high R values can be estimated with reasonable accuracy. The magnitude of ΔKth as a function of colony size is then obtained by summing up the average value of experimentally obtained ΔKeff, th values and the predicted Kcl, th values as a function of colony size. Again, very good agreement of the theoretically predicted ΔKth values with those experimentally obtained has been demonstrated.

On a Ratio of Functions of Exponential Random Variables and Some Applications

Consider L independent and identically distributed exponential random variables (r.vs) X-1, X-2 ,..., X-L and positive scalars b(1), b(2) ,..., b(L). In this letter, we present the probability density function (pdf), cumulative distribution function and the Laplace transform of the pdf of the composite r.v Z = (Sigma(L)(j=1) X-j)(2) / (Sigma(L)(j=1) b(j)X(j)). We show that the r.v Z appears in various communication systems such as i) maximal ratio combining of signals received over multiple channels with mismatched noise variances, ii)M-ary phase-shift keying with spatial diversity and imperfect channel estimation, and iii) coded multi-carrier code-division multiple access reception affected by an unknown narrow-band interference, and the statistics of the r.v Z derived here enable us to carry out the performance analysis of such systems in closed-form.