Hydrogen-bond assisted stabilization of the less favored conformation of a tridentate Schiff base ligand in dinuclear nickel(II) complex: an experimental and theoretical study

The Schiff base ligand, HL (2-[1-(3-methylamino-propylimino)-ethyl]-phenol), the 1:1 condensation product of 2-hydroxy acetophenone and N-methyl-1,3-diaminopropane, has been synthesized and characterized by X-ray crystallography as the perchlorate salt [H2L]ClO4 (1). The structure consists of discrete [H2L](+) cations and perchlorate anions. Two dinuclear Ni-II complexes, [Ni2L2(NO2)(2)] (2), [Ni2L2(NO3)(2)] (3) have been synthesized using this ligand and characterized by single crystal X-ray analyses. Complexes 2 and 3 are centrosymmetric dimers in which the Ni-II ions are in distorted fac- and mer-octahedral environments, respectively, bridged by two mu(2)-phenolate ions of deprotonated ligand, L. The plane of the phenyl rings and the Ni2O2 basal plane are nearly coplanar in 2 but almost perpendicular in 3. We have studied and explained this different behavior using high level DFT calculations (RI-BP86/def2-TZVP level of theory). The conformation observed in 3, which is energetically less favorable, is stabilized via intermolecular non-covalent interactions. Under the excitation of ultraviolet light, characteristic fluorescence of compound 1 was observed; by comparison fluorescence intensity decreases in case of compound 3 and completely quenched in compound 2.

Coordination behavior of pyridylmethylthioether system with cupric chloride and cupric bromide: CS bond cleavage and crystal structures

The coordination behavior of pyridylmethylthioether type of organic moieties having N2S2 donor set [L-1=1,2-bis(2-pyridylmethylthio)ethane, L-2 = 1,3-bis(2-pyridylmethyl-thio)propane and L-3 = 1,4-bis(2-pyridylmethylthio)butane] with copper(II) chloride and copper(II) bromide have been studied in different chemical environments. Copper(II) chloride assisted C-S bond cleavage of the organic moieties leading to the formation of copper(II) picolinate derivatives, whereas, under similar experimental conditions, no C-S bond cleavage was observed in the reaction with copper(II) bromide. The resulted copper(II) complexes isolated from the different mediums have been characterized by spectroscopic and X-ray crystallographic tools.

An LMS style variable tap-length algorithm for structure adaptation

Searching for the optimum tap-length that best balances the complexity and steady-state performance of an adaptive filter has attracted attention recently. Among existing algorithms that can be found in the literature, two of which, namely the segmented filter (SF) and gradient descent (GD) algorithms, are of particular interest as they can search for the optimum tap-length quickly. In this paper, at first, we carefully compare the SF and GD algorithms and show that the two algorithms are equivalent in performance under some constraints, but each has advantages/disadvantages relative to the other. Then, we propose an improved variable tap-length algorithm using the concept of the pseudo fractional tap-length (FT). Updating the tap-length with instantaneous errors in a style similar to that used in the stochastic gradient [or least mean squares (LMS)] algorithm, the proposed FT algorithm not only retains the advantages from both the SF and the GD algorithms but also has significantly less complexity than existing algorithms. Both performance analysis and numerical simulations are given to verify the new proposed algorithm.

Optimum decision delay of the finite-length DFE

This work investigates the optimum decision delay and tap-length of the finite-length decision feedback equalizer. First we show that, if the feedback filter (FBF) length Nb is equal to or larger than the channel memory v and the decision delay Δ is smaller than the feedforward filter (FFF) length Nf, then only the first Δ+1 elements of the FFF can be nonzero. Based on this result we prove that the maximum effective FBF length is equal to the channel memory v, and if Nb ≥ v and Nf is long enough, the optimum decision delay that minimizes the MMSE is Nf-1.

An adaptive linear equalizer with optimum filter length and decision delay

The power of an adaptive equalizer is maximized when the structural parameters including the tap-length and decision delay can be optimally chosen. Although the method for adjusting either the tap-length or decision delay has been proposed, adjusting both simultaneously becomes much more involved as they interact with each other. In this paper, this problem is solved by putting a linear prewhitener before the equalizer, with which the equivalent channel becomes maximum-phase. This implies that the optimum decision delay can be simply ¯xed at the tap-length minus one, while the tap-length can then be chosen using a similar approach as that proposed in our previous work.

Flexible MMSE DFE using length and LAG adaptation

This paper investigates how to choose the optimum tap-length and decision delay for the decision feedback equalizer (DFE). Although the feedback filter length can be set as the channel memory, there is no closed-form expression for the feedforward filter length and decision delay. In this paper, first we analytically show that the two dimensional search for the optimum feedforward filter length and decision delay can be simplified to a one dimensional search, and then describe a new adaptive DFE where the optimum structural parameters can be self-adapted.

Mono-aqua-bridged dinuclear complexes of Cu(II) containing NNO donor Schiff base ligand: Hydrogen-bond-mediated exchange coupling

Two new mono-aqua-bridged dinuclear Cu(II) complexes of tridentate NNO Schiff bases, [Cu-2(mu-H2O)L-2(1)(H2O)(2)](BF4)(2)center dot 2H(2)O (1) and [Cu-2(mu-H2O)L-2(2)(H2O)(2)](BF4)(2)center dot 2H(2)O (2) where HL1 = 2-[1-(2-dimethylamino-ethylimino)-ethyl]-phenol and HL2 =2-[(2-dimethylamino-ethylimino)-methyl]-phenol were synthesized. Both the complexes were characterized by single-crystal X-ray diffraction analyses and variable-temperature magnetic measurements. For both the complexes each Cu(II) ion is in a square-pyramidal environment being bonded to three atoms from the tridentate NNO Schiff base and a terminal H2O molecule in the equatorial plane; a second H2O ligand acts as a bridge between the two Cu(II) centres through the axial positions. Hydrogen bonds between the terminal H2O ligand and the Schiff base of the adjacent centre complete the intra-dimer linkages. Variable-temperature (4-300 K) magnetic susceptibility measurement shows the presence of significant antiferromagnetic coupling for both the complexes (J = -12.2 and -12.5 cm(-1), respectively, for 1 and 2), mediated mainly through the intra-dimer H-bonds.

Lease maturity and initial rent: is there a term structure for UK commercial property leases?

This paper investigates the relationship between lease maturity and rent in commercial property. Over the last decade market-led changes to lease structures, the threat of government intervention and the associated emergence of the Codes of Practice for commercial leases have stimulated growing interest in pricing of commercial property leases. Seminal work by Grenadier (1995) derived a set of hypotheses about the pricing of different lease lengths in different market conditions. Whilst there is a compelling theoretical case for and a strong intuitive expectation of differential pricing of different lease maturities, to date the empirical evidence is inconclusive. Two Swedish studies have found mixed results (Gunnelin and Soderbergh 2003 and Englund et al 2003). In only half the cases is the null hypothesis that lease length has no effect rejected. In the UK, Crosby et al (2003) report counterintuitive results. In some markets, they find that short lease terms are associated with low rents, whilst in others they are associated with high rents. Drawing upon a substantial database of commercial lettings in central London (West End and City of London) over the last decade, we investigate the relationship between rent and lease maturity. In particular, we test whether a building quality variable omitted in previous studies provides empirical results that are more consistent with the theoretical and intuitive a priori expectations. It is found that initial leases rates are upward sloping with the lease term and that this relationship is constant over time.

The persistence of real estate fund performance

This paper examines the short and long-term persistence of tax-exempt real estate funds in the UK through the use of winner-loser contingency table methodology. The persistence tests are applied to a database of varying numbers of funds from a low of 16 to a high of 27 using quarterly returns over the 12 years from 1990 Q1 to 2001 Q4. The overall conclusion is that the real estate funds in the UK show little evidence of persistence in the short-term (quarterly and semi-annual data) or for data over a considerable length of time (bi-annual to six yearly intervals). In contrast, the results are better for annual data with evidence of significant performance persistence. Thus at this stage, it seems that an annual evaluation period, provides the best discrimination of the winner and loser phenomenon in the real estate market. This result is different from equity and bond studies, where it seems that the repeat winner phenomenon is stronger over shorter periods of evaluation. These results require careful interpretation, however, as the results show that when only small samples are used significant adjustments must be made to correct for small sample bias and second the conclusions are sensitive to the length of the evaluation period and specific test used. Nonetheless, it seems that persistence in performance of real estate funds in the UK does exist, at least for the annual data, and it appears to be a guide to beating the pack in the long run. Furthermore, although the evidence of persistence in performance for the overall sample of funds is limited, we have found evidence that two funds were consistent winners over this period, whereas no one fund could be said to be a consistent loser.

Effects of utterance length on lip kinematics in aphasia

Most existing models of language production and speech motor control do not explicitly address how language requirements affect speech motor functions, as these domains are usually treated as separate and independent from one another. This investigation compared lip movements during bilabial closure between five individuals with mild aphasia and five age and gender-matched control speakers when the linguistic characteristics of the stimuli were varied by increasing the number of syllables. Upper and lower lip movement data were collected for mono-, bi- and tri-syllabic nonword sequences using an AG 100 EMMA system. Each task was performed under both normal and fast rate conditions. Single articulator kinematic parameters (peak velocity, amplitude, duration,and cyclic spatio-temporal index) were measured to characterize lip movements. Results revealed that compared to control speakers, individuals with aphasia showed significantly longer movement duration and lower movement stability for longer items (bi- and tri-syllables). Moreover, utterance length affected the lip kinematics, in that the monosyllables had smaller peak velocities, smaller amplitudes and shorter durations compared to bi- and trisyllables, and movement stability was lowest for the trisyllables. In addition, the rate-induced changes (smaller amplitude and shorter duration with increased rate) were most prominent for the short items (i.e., monosyllables). These findings provide further support for the notion that linguistic changes have an impact on the characteristics of speech movements, and that individuals with aphasia are more affected by such changes than control speakers.