Ternary metal complexes of anionic and neutral pyridoxine (vitamin B6) with 2,2'-bipyridine. Syntheses and x-ray structures of (pyridoxinato)bis(2,2'-bipyridyl)cobalt(III) perchlorate and chloro(2,2'-bipyridyl)(pyridoxine)copper(II) perchlorate hydrate

Ternary metal complexes involving vitamin B6 with formulas [CO",(PN-H)](anCdI [OC)'(bpy)(PN)Cl]C10(.bpHy 0 = 2,2'-bipyridine, PN = neutral pyridoxine, PN-H = anionic pyridoxine) have been prepared for the first time and characterized by means of magnetic and spectroscopic measurements. The crystal structures of the compounds have also been determined. [CO(PN-H)](CcryIsOta,l)lize s in the space group P2,/c with a = 18.900 (3) A, b = 8.764 (1) A, c = 20.041 (2) A,p = 116.05 (l)', and Z = 4 and [Cu(bpy)(PN)C1]C104-H20in the space group Pi with a = 12.136 (5) A, b = 13.283 (4) A,c = 7.195 (2) A, a = 96.91 (Z)', 0 = 91.25 (3)', y = 71.63 (3)', and Z = 2. The structures were solved by the heavy-atom method and refined by least-squares techniques to R values of 0.080 and 0.042 for 3401 and 2094 independent reflections, respectively. Both structures consist of monomeric units. The geometry around Co(II1) is octahedral and around Cu(I1) is distorted square pyramidal. In [CO(PN-H)]t(wCo IoxOy~ge)n~s ,fro m phenolic and 4-(hydroxymethyl) groups of PN-H and two nitrogens from each of two bpy's form the coordination sphere. In [Cu(bpy)(PN)C1]C104.H20o ne PN and one bpy, with the same donor sites, act as bidentate chelates in the basal plane, with a chloride ion occupying the apical position. In both structures PN and PN-H exist in the tautomeric form wherein pyridine N is protonated and phenolic 0 is deprotonated. However, a novel feature of the cobalt compound is that PN-H is anionic due to the deprotonation of the 4-(hydroxymethyl) group. The packing in both structures is governed by hydrogen bonds, and in the copper compound partial stacking of bpy's at a distance of -3.55 also adds to the stability of the system. Infrared, NMR, and ligand field spectroscopic results and magnetic measurements are interpreted in light of the structures.

Performance of slotted ALOHA satellite channels with finite buffer

The behaviour of the slotted ALOHA satellite channel with a finite buffer at each of the user terminals is studied. Approximate relationships between the queuing delay, overflow probabilities and buffer size are derived as functions of the system input parameters (i.e. the number of users, the traffic intensity, the transmission and the retransmission probabilities) for two cases found in the literature: the symmetric case (same transmission and retransmission probabilities), and the asymmetric case (transmission probability far greater than the retransmission probability). For comparison, the channel performance with an infinite buffer is also derived. Additionally, the stability condition for the system is defined in the latter case. The analysis carried out in the paper reveals that the queuing delays are quite significant, especially under high traffic conditions.

Phased-Mission Analysis for Evaluating the Effectiveness of Aerospace Computing-Systems

Effectiveness evaluation of aerospace fault-tolerant computing systems used in a phased-mission environment is rather tricky and difficult because of the interaction of its several degraded performance levels with the multiple objectives of the mission and the use environment. Part I uses an approach based on multiobjective phased-mission analysis to evaluate the effectiveness of a distributed avionics architecture used in a transport aircraft. Part II views the computing system as a multistate s-coherent structure. Lower bounds on the probabilities of accomplishing various levels of performance are evaluated.

Iron(II) and iron(III) complexes of 2,4-dithiobiuret

Ferrous and ferric complexes of 2,4-dithiobiuret (Dtb) of the type Fe(Dtb)m Xn where m, n = 1-3, and X = CI–, Br–, I– and SO 4 2– , and a neutral Fe(Dtb-H)2 complex have been synthesized and characterised by elemental analyses, magnetic susceptibility, i.r., electronic and Mössbauer spectroscopic studies. From its i.r. spectrum Dtb was found to act as a S,S-coordinating bidentate chelate. The magnetic moment, electronic and Massbauer spectra are consistent with a low spin distorted octahedral structure for the ferric complexes and a high spin form for ferrous complexes.

Multiaction learning automata possessing ergodicity of the mean

Multiaction learning automata which update their action probabilities on the basis of the responses they get from an environment are considered in this paper. The automata update the probabilities according to whether the environment responds with a reward or a penalty. Learning automata are said to possess ergodicity of the mean if the mean action probability is the state probability (or unconditional probability) of an ergodic Markov chain. In an earlier paper [11] we considered the problem of a two-action learning automaton being ergodic in the mean (EM). The family of such automata was characterized completely by proving the necessary and sufficient conditions for automata to be EM. In this paper, we generalize the results of [11] and obtain necessary and sufficient conditions for the multiaction learning automaton to be EM. These conditions involve two families of probability updating functions. It is shown that for the automaton to be EM the two families must be linearly dependent. The vector defining the linear dependence is the only vector parameter which controls the rate of convergence of the automaton. Further, the technique for reducing the variance of the limiting distribution is discussed. Just as in the two-action case, it is shown that the set of absolutely expedient schemes and the set of schemes which possess ergodicity of the mean are mutually disjoint.

Improved optical character recognition by matched filtering

The effectiveness of linear matched filters for improved character discrimination in presence of random noise and poorly defined characters has been investigated. We have found that although the performance of the filter in presence of random noise is reasonably good (16 dB gain in signal-to-noise-ratio) its performance is poor when the unknown character is distorted (linear shift and rotation).

Improved optical character recognition by matched filtering

The effectiveness of linear matched filters for improved character discrimination in presence of random noise and poorly defined characters has been investigated. We have found that although the performance of the filter in presence of random noise is reasonably good (16 dB gain in signal-to-noise-ratio) its performance is poor when the unknown character is distorted (linear shift and rotation).

Unusual effects of anisotropic bonding in Cu(II) and Ni(II) oxides with K2NiF4 structure

Geometric constraints present in A2BO4 compounds with the tetragonal-T structure of K2NiF4 impose a strong pressure on the B---OII---B bonds and a stretching of the A---OI---A bonds in the basal planes if the tolerance factor is t congruent with RAO/√2 RBO < 1, where RAO and RBO are the sums of the A---O and B---O ionic radii. The tetragonal-T phase of La2NiO4 becomes monoclinic for Pr2NiO4, orthorhombic for La2CuO4, and tetragonal-T′ for Pr2CuO4. The atomic displacements in these distorted phases are discussed and rationalized in terms of the chemistry of the various compounds. The strong pressure on the B---OII---B bonds produces itinerant σ*x2−y2 bands and a relative stabilization of localized dz2 orbitals. Magnetic susceptibility and transport data reveal an intersection of the Fermi energy with the d2z2 levels for half the copper ions in La2CuO4; this intersection is responsible for an intrinsic localized moment associated with a configuration fluctuation; below 200 K the localized moment smoothly vanishes with decreasing temperature as the d2z2 level becomes filled. In La2NiO4, the localized moments for half-filled dz2 orbitals induce strong correlations among the σ*x2−y2 electrons above Td reverse similar, equals 200 K; at lower temperatures the σ*x2−y2 electrons appear to contribute nothing to the magnetic susceptibility, which obeys a Curie-Weiss law giving a μeff corresponding to S = 1/2, but shows no magnetic order to lowest temperatures. These surprising results are verified by comparison with the mixed systems La2Ni1−xCuxO4 and La2−2xSr2xNi1−xTixO4. The onset of a charge-density wave below 200 K is proposed for both La2CuO4 and La2NiO4, but the atomic displacements would be short-range cooperative in mixed systems. The semiconductor-metallic transitions observed in several systems are found in many cases to obey the relation Ea reverse similar, equals kTmin, where varrho = varrho0exp(−Ea/kT) and Tmin is the temperature of minimum resistivity varrho. This relation is interpreted in terms of a diffusive charge-carrier mobility with Ea reverse similar, equals ΔHm reverse similar, equals kT at T = Tmin.

Statistical significance of sequential firing patterns in multi-neuronal spike trains

Sequential firings with fixed time delays are frequently observed in simultaneous recordings from multiple neurons. Such temporal patterns are potentially indicative of underlying microcircuits and it is important to know when a repeatedly occurring pattern is statistically significant. These sequences are typically identified through correlation counts. In this paper we present a method for assessing the significance of such correlations. We specify the null hypothesis in terms of a bound on the conditional probabilities that characterize the influence of one neuron on another. This method of testing significance is more general than the currently available methods since under our null hypothesis we do not assume that the spiking processes of different neurons are independent. The structure of our null hypothesis also allows us to rank order the detected patterns. We demonstrate our method on simulated spike trains.

Performance of slotted ALOHA satellite channels with finite buffer

The behaviour of the slotted ALOHA satellite channel with a finite buffer at each of the user terminals is studied. Approximate relationships between the queuing delay, overflow probabilities and buffer size are derived as functions of the system input parameters (i.e. the number of users, the traffic intensity, the transmission and the retransmission probabilities) for two cases found in the literature: the symmetric case (same transmission and retransmission probabilities), and the asymmetric case (transmission probability far greater than the retransmission probability). For comparison, the channel performance with an infinite buffer is also derived. Additionally, the stability condition for the system is defined in the latter case. The analysis carried out in the paper reveals that the queuing delays are quite significant, especially under high traffic conditions.

Location of concentrators in a computer communication network: a stochastic automation search method

The following problem is considered. Given the locations of the Central Processing Unit (ar;the terminals which have to communicate with it, to determine the number and locations of the concentrators and to assign the terminals to the concentrators in such a way that the total cost is minimized. There is alao a fixed cost associated with each concentrator. There is ail upper limit to the number of terminals which can be connected to a concentrator. The terminals can be connected directly to the CPU also In this paper it is assumed that the concentrators can bo located anywhere in the area A containing the CPU and the terminals. Then this becomes a multimodal optimization problem. In the proposed algorithm a stochastic automaton is used as a search device to locate the minimum of the multimodal cost function . The proposed algorithm involves the following. The area A containing the CPU and the terminals is divided into an arbitrary number of regions (say K). An approximate value for the number of concentrators is assumed (say m). The optimum number is determined by iteration later The m concentrators can be assigned to the K regions in (mk) ways (m > K) or (km) ways (K>m).(All possible assignments are feasible, i.e. a region can contain 0,1,…, to concentrators). Each possible assignment is assumed to represent a state of the stochastic variable structure automaton. To start with, all the states are assigned equal probabilities. At each stage of the search the automaton visits a state according to the current probability distribution. At each visit the automaton selects a 'point' inside that state with uniform probability. The cost associated with that point is calculated and the average cost of that state is updated. Then the probabilities of all the states are updated. The probabilities are taken to bo inversely proportional to the average cost of the states After a certain number of searches the search probabilities become stationary and the automaton visits a particular state again and again. Then the automaton is said to have converged to that state Then by conducting a local gradient search within that state the exact locations of the concentrators are determined This algorithm was applied to a set of test problems and the results were compared with those given by Cooper's (1964, 1967) EAC algorithm and on the average it was found that the proposed algorithm performs better.

Pyridine-1-oxide complexes of lanthanide iodides

Pyridine-1-oxide complexes of lanthanide iodides of the formulaLn(PyO)8I3 whereLn=La, Pr, Nd, Tb, Dy, Er, and Yb have been prepared and characterised by analyses, molecular weight, conductance, infrared and proton NMR data. Proton NMR and IR data have shown the coordination of the ligand to the metal through the oxygen atom of the N–O group. NMR data have been interpreted in terms of a distorted square antiprismatic geometry in solution.

New ternary copper(II) complexes of L-alanine and heterocyclic bases: DNA binding and oxidative DNA cleavage activity

Four new ternary copper(II) complexes of alpha-amino acid having polypyridyl bases of general formulation [Cu(L-ala)(B)(H2O)](X)(1-4), where L-ala is L-alanine, B is an N,N-donor heterocyclic base, viz. 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2) and 5,6-phenanthroline dione (dione, 3), dipyrido[3,2:2',3'-f] quinoxaline (dpq, 4), and X = ClO4-/NO3- are synthesized, characterized by various spectroscopic and X-ray crystallographic methods. The complexes show a distorted square-pyramidal (4 + 1) CuN3O2 coordination geometry. The one-electron paramagnetic complexes (1-4) display a low energy d-d band near 600 nm in aqueous medium and show a quasi-reversible cyclic voltammetric response due to one-electron Cu(II)/Cu(I) reduction near - 100 mV (versus SCE) in DMF-0.1 M TBAP. Binding interactions of the complexes with calf thymus DNA (CT-DNA) were investigated by UV-Vis absorption titration, ethidium bromide displacement assay, viscometric titration experiment and DNA melting studies. All the complexes barring the complexes 1 and 3 are avid binder to the CT-DNA in the DNA minor groove giving an order: 4 > 2 >>>1, 3. The complexes 2 and 4 show appreciable chemical nuclease activity in the presence of 3-mercaptopropionic acid (MPA) as a reducing agent. Hydroxyl radical was investigated to be the DNA cleavage active species. Control experiments in the presence of distamycin-A show primarily minor groove-binding propensity for the complexes 2 and 4 to the DNA.

Cochannel Interference in Partially Coherent Communication

Effects of cochannel interference and synchronization error of the carrier phase on the probability of error in binary communications are considered. Several bounds on the probability of error are proposed. The bounds are easy to compute and do not require complete statistical characterization of the errors. They turn out to be simple linear combinations of error probabilities with no cochannel interferences and no phase errors. Several illustrative examples are given which show that the bounds can be tight.

X-ray crystal structure of a ternary copper(II) vitamin B6 complex, hydroxo(2,2'-bipyridyl)(pyridoxinato) copper(II) monohydrate. A rare example of monodentate coordination of copper(II) by the hydroxyl ion

A ternary metal complex involving Vitamin B6 with the formula [Cu(bipy)(pn) (OH)]H2O (bipy = 2,2'²-bipyridine, PN = anionic pyridoxine) has been synthesized and studied in the solid state by means of spectroscopy and X-ray crystallography. The geometry around copper(II) is distorted square pyramidal, two oxygens from phenolic and 4-(hydroxymethyl) groups of pn, two nitrogens from bipy and an axial OH- ion forming the coordination sphere. In this structure pn exists in a new anionic form with deprotonation of the phenolic group. The structure also provides a rare example of monodentate hydroxyl coordination to copper.