Investigation of inter-ion interactions in N,N,N',N'-tetramethylethylenediammonium dithiocyanate via experimental and theoretical charge density studies

The crystal structure of the N,N,N',N'-tetramethylethylenediammonium dithiocyanate salt has been examined by experimental charge density studies from high-resolution X-ray diffraction data. The corresponding results are compared with multipole refinements, using theoretical structure factors obtained from a periodic density functional theory calculation at the B3LYP level with a 6-31G** basis set. The salt crystallizes in space group P (1) over bar and contains only a single ion pair with an inversion center in the cation. The salt has thus one unique classical N+-H center dot center dot center dot(NCS)(-) hydrogen bond but also has six other weaker interactions: four C-H center dot center dot center dot S, one C-H center dot center dot center dot N, and one C-H center dot center dot center dot C-pi. The nature of all these interactions has been examined topologically using Bader's quantum theory of "atoms in molecules" and all eight of the Koch-Popelier criteria. The experimental and theoretical approaches agree well and both show that the inter-ion interactions, even in this simplest of systems, play an integrated and complex role in the packing of the ions in the crystal. Electrostatic potential maps are derived from experimental charge densities. This is the first time such a system has been examined in detail by these methods.

Ion pairs in non-redundant protein structures

Ion pairs contribute to several functions including the activity of catalytic triads, fusion of viral membranes, stability in thermophilic proteins and solvent-protein interactions. Furthermore, they have the ability to affect the stability of protein structures and are also a part of the forces that act to hold monomers together. This paper deals with the possible ion pair combinations and networks in 25% and 90% non-redundant protein chains. Different types of ion pairs present in various secondary structural elements are analysed. The ion pairs existing between different subunits of multisubunit protein structures are also computed and the results of various analyses are presented in detail. The protein structures used in the analysis are solved using X-ray crystallography, whose resolution is better than or equal to 1.5 angstrom and R-factor better than or equal to 20%. This study can, therefore, be useful for analyses of many protein functions. It also provides insights into the better understanding of the architecture of protein structure.

Jointly optimal power control and routing for a single cell, dense, ad hoc wireless network

We consider a dense, ad hoc wireless network confined to a small region, such that direct communication is possible between any pair of nodes. The physical communication model is that a receiver decodes the signal from a single transmitter, while treating all other signals as interference. Data packets are sent between source-destination pairs by multihop relaying. We assume that nodes self-organise into a multihop network such that all hops are of length d meters, where d is a design parameter. There is a contention based multiaccess scheme, and it is assumed that every node always has data to send, either originated from it or a transit packet (saturation assumption). In this scenario, we seek to maximize a measure of the transport capacity of the network (measured in bit-meters per second) over power controls (in a fading environment) and over the hop distance d, subject to an average power constraint. We first argue that for a dense collection of nodes confined to a small region, single cell operation is efficient for single user decoding transceivers. Then, operating the dense ad hoc network (described above) as a single cell, we study the optimal hop length and power control that maximizes the transport capacity for a given network power constraint. More specifically, for a fading channel and for a fixed transmission time strategy (akin to the IEEE 802.11 TXOP), we find that there exists an intrinsic aggregate bit rate (Theta(opt) bits per second, depending on the contention mechanism and the channel fading characteristics) carried by the network, when operating at the optimal hop length and power control. The optimal transport capacity is of the form d(opt)((P) over bar (t)) x Theta(opt) with d(opt) scaling as (P) over bar (1/eta)(t), where (P) over bar (t) is the available time average transmit power and eta is the path loss exponent. Under certain conditions on the fading distribution, we then provide a simple characterisation of the optimal operating point.

High-rate, Single-Symbol Decodable Distributed STBCs for Partially-Coherent Cooperative Networks

Space-time block codes (STBCs) that are single-symbol decodable (SSD) in a co-located multiple antenna setting need not be SSD in a distributed cooperative communication setting. A relay network with N relays and a single source-destination pair is called a partially-coherent relay channel (PCRC) if the destination has perfect channel state information (CSI) of an the channels and the relays have only the phase information of the source-to-relay channels. In our earlier work, we had derived a set of necessary and sufficient conditions for a distributed STBC (DSTBC) to be SSD for a PCRC. Using these conditions, in this paper we show that the possibility of channel phase compensation operation at the relay nodes using partial CSI at the relays increases the possible rate of SSD DSTBCs from 2/N when the relays do not have CSI to 1/2, which is independent of N. We also show that when a DSTBC is SSD for a PCRC, then arbitrary coordinate interleaving of the in-phase and quadrature-phase components of the variables does not disturb its SSD property. Using this property we are able to construct codes that are SSD and have higher rate than 2/N but giving full diversity only for signal constellations satisfying certain conditions.

Conditional Probability-Based Significance Tests for Sequential Patterns in Multineuronal Spike Trains

We consider the problem of detecting statistically significant sequential patterns in multineuronal spike trains. These patterns are characterized by ordered sequences of spikes from different neurons with specific delays between spikes. We have previously proposed a data-mining scheme to efficiently discover such patterns, which occur often enough in the data. Here we propose a method to determine the statistical significance of such repeating patterns. The novelty of our approach is that we use a compound null hypothesis that not only includes models of independent neurons but also models where neurons have weak dependencies. The strength of interaction among the neurons is represented in terms of certain pair-wise conditional probabilities. We specify our null hypothesis by putting an upper bound on all such conditional probabilities. We construct a probabilistic model that captures the counting process and use this to derive a test of significance for rejecting such a compound null hypothesis. The structure of our null hypothesis also allows us to rank-order different significant patterns. We illustrate the effectiveness of our approach using spike trains generated with a simulator.

Graphene-like two-dimensional ionic boron with double dirac cones at ambient condition

Recently, partially ionic boron (γ-B28) has been predicted and observed in pure boron, in bulk phase and controlled by pressure [Nature, 457 (2009) 863]. By using ab initio evolutionary structure search, we report the prediction of ionic boron at a reduced dimension and ambient pressure, namely, the two-dimensional (2D) ionic boron. This 2D boron structure consists of graphene-like plane and B2 atom pairs, with the P6/mmm space group and 6 atoms in the unit cell, and has lower energy than the previously reported α-sheet structure and its analogues. Its dynamical and thermal stability are confirmed by the phonon-spectrum and ab initio molecular dynamics simulation. In addition, this phase exhibits double Dirac cones with massless Dirac fermions due to the significant charge transfer between the graphene-like plane and B2 pair that enhances the energetic stability of the P6/mmm boron. A Fermi velocity (vf) as high as 2.3 x 106 m/s, which is even higher than that of graphene (0.82 x 106 m/s), is predicted for the P6/mmm boron. The present work is the first report of the 2D ionic boron at atmospheric pressure. The unique electronic structure renders the 2D ionic boron a promising 2D material for applications in nanoelectronics.

Organometallic chemistry of diphosphazanes. Part 26. Ruthenium hydride complexes of chiral and achiral diphosphazane ligands and asymmetric transfer hydrogenation reactions

The half-sandwhich ruthenium chloro complexes bearing chelated diphosphazane ligands, [(eta(5)-Cp)RuCl{kappa(2)-P,P-(RO)(2)PN(Me)P(OR)(2)}] [R = C6H3Me2-2,6] (1) and [(eta(5)-Cp*)RuCl{kappa(2)-P, P-X2PN(R)PYY'}] [R = Me, X = Y = Y' = OC6H5 (2); R = CHMe2, X-2 = C20H12O2, Y = Y' = OC6H5 (3) or OC6H4'Bu-4 (4)] have been prepared by the reaction of CpRu(PPh3)(2)Cl with (RO)(2)PN(Me)P(OR)(2) [R = C6H3Me2-2,6 (L-1)] or by the reaction of [Cp*RuCl2](n) with X2PN(R)PYY' in the presence of zinc dust. Among the four diastereomers (two enantiomeric pairs) possible for the "chiral at metal" complexes 3 and 4, only two diastereomers (one enantiomeric pair) are formed in these reactions. The complexes 1, 2, 4 and [(eta(5)-Cp)RuCl {kappa(2)-P,P-Ph2PN((S)-*CHMePh)PPhY)] [Y = Ph (5) or N2C3HMe2-3,5 (SCSPRRu)-(6)] react with NaOMe to give the corresponding hydride complexes [(eta(5) -Cp)RuH {kappa(2)-P,P-(RO)(2)PN(Me)P(OR)(2)}] (7), [(eta(5)-Cp*)RuH {kappa(2)-P,P'-X2PN(R)PY2)] [R = Me, X = Y = OC6H5 (8); R = CHMe2, X-2 = C20H12O2, Y = OC6H4'Bu-4 (9)] and [(eta(5) -Cp)RuH(kappa(2)-P, P-Ph2PN((S)-*CHMePh)PPhY)][Y =Ph (10) or N2C3HMe2-3,5 (SCSPRRu)(11a) and (SCSPSRu)-(11b)]. Only one enantiomeric pair of the hydride 9 is obtained from the chloro precursor 4 that bears sterically bulky substituents at the phosphorus centers. On the other hand, the optically pure trichiral complex 6 that bears sterically less bulky substituents at the phosphorus gives a mixture of two diastereomers (11a and 11b). Protonation of complex 7 using different acids (HX) gives a mixture of [(eta(5)- Cp)Ru(eta(2)-H-2){kappa(2)-P, P-(RO)(2)PN(Me)P(OR)(2))]X (12a) and [(eta(5)-Cp)Ru(H)(2){kappa(2)-P, P-(RO)(2)PN(Me)P(OR)(2)}]X (12b) of which 12a is the major product independent of the acid used; the dihydrogen nature of 12a is established by T, measurements and also by synthesizing the deuteride analogue 7-D followed by protonation to obtain the D-H isotopomer. Preliminary investigations on asymmetric transfer hydrogenation of 2-acetonaphthone in the presence of a series of chiral diphosphazane ligands show that diphosphazanes in which the phosphorus centers are strong pi-acceptor in character and bear sterically bulky substituents impart moderate levels of enantioselectivity. Attempts to identify the hydride intermediate involved in the asymmetric transfer hydrogenation by a model reaction suggests that a complex of the type, [Ru(H)(Cl){kappa(2)-P,P-X2PN(R)PY2)(solvent)(2)] could be the active species in this transformation. (c) 2007 Elsevier B.V. All rights reserved.

Simplified theory of optical nonlinearities in spin-polarized bulk GaAs

Apart from their intrinsic physical interest, spin-polarized many-body effects are expected to be important to the working of spintronic devices. A vast literature exists on the effects of a spin-unpolarized electron-hole plasma on the optical properties of a semiconductor. Here, we include the spin degree of freedom to model optical absorption of circularly polarized light by spin-polarized bulk GaAs. Our model is easy to implement and does not require elaborate numerics, since it is based on the closed-form analytical pair-equation formula that is valid in 3d. The efficacy of our approach is demonstrated by a comparison with recent experimental data.

Fluorescent resonant excitation energy transfer in linear polyenes

We have studied the dynamics of excitation transfer between two conjugated polyene molecules whose intermolecular separation is comparable to the molecular dimensions. We have employed a correlated electron model that includes both the charge-charge, charge-bond, and bond-bond intermolecular electron repulsion integrals. We have shown that the excitation transfer rate varies as inverse square of donor-acceptor separation R-2 rather than as R-6, suggested by the Foumlrster type of dipolar approximation. Our time-evolution study alsom shows that the orientational dependence on excitation transfer at a fixed short donor-acceptor separation cannot be explained by Foumlrster type of dipolar approximation beyond a certain orientational angle of rotation of an acceptor polyene with respect to the donor polyene. The actual excitation transfer rate beyond a certain orientational angle is faster than the Foumlrster type of dipolar approximation rate. We have also studied the excitation transfer process in a pair of push-pull polyenes for different push-pull strengths. We have seen that, depending on the push-pull strength, excitation transfer could occur to other dipole coupled states. Our study also allows for the excitation energy transfer to optically dark states which are excluded by Foumlrster theory since the one-photon transition intensity to these states (from the ground state) is zero.

Linear transconductor with flipped voltage follower in 130 nm CMOS

This paper presents a modified design method for linear transconductor circuit in 130 nm CMOS technology to improve linearity, robustness against process induced threshold voltage variability and reduce harmonic distortion. Source follower in the adaptively biased differential pair (ABDP) linear transconductor circuit is replaced with flipped voltage follower to improve the efficiency of the tail current source, which is connected to a conventional differential pair. The simulation results show the performance of the modified circuit also has better speed, noise performance and common mode rejection ratio compared to the ABDP circuit.

Slogans of Change : Three Outlooks on Finnish Television

The study Slogans of Change. Three Outlooks on Finnish Television Contents is concerned with alleged changes of television contents during the 1990s and 2000s, such as dumbing down, tabloidisation, entertainisation , and the like. Specifically, the focus is on the ways these changes might manifest in Finnish television. The aim of the study has been threefold: 1. To operationalise public and academic discussions about changes via specific slogans emerging from the debates; 2. Consequently, to study the slogans empirically and reflect on the findings with earlier research, including studies on institutional and audience-related aspects; 3. Finally, to suggest what the findings might mean regarding discussions about television s role, and what kinds of slogans or concepts might best serve future discussions and research. The empirical outlooks presented in this study offer analyses with three different sets of opposing slogans of change. The outlooks also follow three different traditions of the study of television. The first outlook focuses on quantity, as it gives a longitudinal (1993-2004), macro-level view on programme structures. The methodological approach is derived from media economic and policy studies. The claims that frame the analysis are convergence versus diversification of programme structures. The second outlook provides quantitative and qualitative views on the characteristics and quality  the term signifying essence as well as worth  of Finnish television journalism during sample weeks from the years 2002 and 2003. This outlook follows the traditions of quantitative content analysis found in journalism studies coupled with descriptive qualitative content analyses. The slogans reflected in this section are the lightening or widening of journalism. The third outlook narrows down the material and focuses at a micro-level on form; that is, communicative conventions in a small array of selected programmes in 1993, 2000 and during 2002-2004. The analyses have been inspired by the method of conversation analysis of verbal interaction, and coupled with qualitative close readings, with the focus of different communicative situations in the programmes. The catchphrases employed in this part are emotainment versus democratainment, coupled with more specific claims of discursive hybridisation and conversationalisation. The findings depict that, empirically, changes in Finnish television contents are not clear linear trends and cannot easily be moulded into neat slogans. The quantitative outlook on programme output during 1993-2004 depicts a tendency towards differentiation of channels, paving the way for the multi-channel digital system. The change in programme structures, however, is not dramatic on the level of total output. The second outlook suggests that the dualistic concepts, such as the pair information-entertainment, are not sufficient in understanding the array and changes of programmes that could be called journalism. The outlook on communicative conventions highlights hybridisation in the manner of television talk and its relation to broader debates on contents. Despite the three dissimilar empirical approaches, unifying aspects emerge. The outlooks suggest, albeit in different ways, tendencies toward distinction and polarisation. This study proposes that in order to facilitate a more nuanced understanding of the changes in television contents, dualistic slogans should be replaced with a multi-dimensional understanding of the concept of diversity.

Modular design of synthetic protein mimics. Crystal structures, assembly, and hydration of two 15- and 16-residue apolar, leucyl-rich helical peptides

Two IS- and 16-residue peptides containing a-aminoisobutyric acid (Aib) have been synthesized, as part of a strategy to construct stereochemically rigid peptide helices, in a modular approach to design of protein mimics. The peptides Boc-(Val-Ala-Leu-Aib),-OMe ( I ) and Boc-Val-Ala-Leu-Aib-Val-Ala-Leu-(Val-Ala-Leu-Aib()11z)- OhaMvee been crystallized.Both crystals are stable only in the presence of mother liquor or water. The crystal data are as follows. I: C78H140N16019~2H20,P2,, a = 16.391 (3) A, b = 16.860 (3) A, c = 18.428 (3) A, p = 103.02 (I)O, Z = 2, R = 9.6% for 3445 data with lFol >30(F), resolution 0.93 A. 11: C7,Hl,,N,S018.7.5H,0, C2221, a = 18.348 ( 5 ) A, b = 47.382 (1 1) A, c = 24.157 ( 5 ) A, Z =8, R = l0,6%, for 3147 data with lFol > 3a(F), resolution 1.00 A. The 15-residue peptide (11) is entirely a helical, while the 16-residue peptide ( I ) has a short segment of 310 helix at the N terminus. The packing of the helices in the crystals is rather incfficicnt with no particular attractions between Leu-Leu side chains, or any other pair. Both crystals have fairly large voids, which are filled with water molecules in a disordered fashion. Water molecule sites near the polar head-to-tail regions are well detcrmined, those closer to the hydrophobic side chains less so and a number of possible water sites in the remaining "empty" space are not determined. No interdigitation of Leu side chains is observed in the crystal as is hypothesized in the "leucine zipper" class of DNA binding proteins.

Simplified theory of optical nonlinearities in spin-polarized bulk GaAs

Apart from their intrinsic physical interest, spin-polarized many-body effects are expected to be important to the working of spintronic devices. A vast literature exists on the effects of a spin-unpolarized electron-hole plasma on the optical properties of a semiconductor. Here, we include the spin degree of freedom to model optical absorption of circularly polarized light by spin-polarized bulk GaAs. Our model is easy to implement and does not require elaborate numerics, since it is based on the closed-form analytical pair-equation formula that is valid in 3d. The efficacy of our approach is demonstrated by a comparison with recent experimental data.

On the performance analysis of a class of neuron circuits

A new performance metric, Peak-Error Ratio (PER) has been presented to benchmark the performance of a class of neuron circuits to realize neuron activation function (NAF) and its derivative (DNAF). Neuron circuits, biased in subthreshold region, based on the asymmetric cross-coupled differential pair configuration and conventional configuration of applying small external offset voltage at the input have been compared on the basis of PER. It is shown that the technique of using transistor asymmetry in a cross-coupled differential pair performs on-par with that of applying external offset voltage. The neuron circuits have been experimentally prototyped and characterized as a proof of concept on the 1.5 mu m AMI technology.

Reversible electrochemistry of cytochrome c on recompressed, binderless exfoliated graphite electrodes

The direct electrochemistry of cytochrome c (cyt-c) has been investigated on exfoliated graphite (EG) electrodes. The as-polished and roughened (using SiC emery sheet) EG surfaces are inactive for the direct electron transfer. However, when the EG electrode was sonicated before the experiment, a pair of redox waves were obtained for freely diffusing cyt-c in the solution phase. The formal potential was found to be 0.01 V (vs. SCE) in 0.1 M phosphate buffer at a pH of 7.1. The electrochemical response for the adsorbed cyt-c on sonicated EG electrodes, which is shown to have carbonyl functional groups on its surface, shows nearly reversible voltammograms in the same electrolyte. However, the formal potential in the adsorbed state is more negative than that observed for the solution phase cyt-c. A structure based on an open heme conformation proposed by Hildebrandt and Stockburger is probably present on the EG surface. It is suggested that the electrochemistry at the EG electrode is essentially governed by favourable electrostatic interactions.