Conformations of dehydrophenylalanine containing peptides. NMR studies on three tripeptides with a central dehydrophenylalanyl residue.

Three tripeptides containing a central Z-dehydrophenylalanine residue (Δz-Phe), Boc-L-Phe-Δz-Phe-X-OMe (X = L-Val 1, L-Leu 2 and X = L-Ala 3) have been synthesized and their solution conformations investigated by 270 MHz 1H NMR spectroscopy. In all three peptides, conformations involving the X residue NH in an intramolecular hydrogen bond were favoured in CDCl3 solutions. Studies of the nuclear Overhauser effect (NOE) provided support for a Type II β turn conformation in these peptides with Phe and Δz-Phe occupying the i + 1 and i + 2 positions, respectively. Significantly different conformations lacking any intramolecular hydrogen bonds were observed for peptide 1 in (CD3)2SO. NOE results were consistent with a significant population of molecules having semi-extended conformations (ø > 100°) at the Δz-Phe residue.

A nonhelical, multiple β-turn conformation in a glycine-rich heptapeptide fragment of trichogin A IV containing a single central α-aminoisobutyric acid residue

The conformational properties of the protected seven-residue C-terminal fragment the lipopeptaibol antibiotic Trichogin A IV (Boc-Gly-Gly-Leu-Aib-Gly-Ile-Leu-OMe) has been examined in CDCl3 and (CD3)2SO by 1H-nmr. Evidence for a multiple β-turn conformation [type I′ at Gly(1)-Gly(2), type II at Leu(3)-Aib(4), and a type I′ at Aib(4)-Gly(5)] suggests that Leu(3) has preferred an extended or semiextended conformation over a helical conformation in CDCl3. This structure is thus in contrast to earlier observations of seven-residue peptides containing a single central Aib preferring helical conformations in both solution and crystalline slates. A structural transition to a frayed right-handed helix is absented in (CD3)2SO. These results suggest that nonhelical conformations may be important in Gly-rich peptides containing Aib. Further, the presence of amino acids with contradictory influences on backbone conformational freedom can lead to well-defined conformational transitions even in small peptides

LIN28B, LIN28A, KISS1, and KISS1R in idiopathic central precocious puberty

Abstract Background Pubertal timing is a strongly heritable trait, but no single puberty gene has been identified. Thus, the genetic background of idiopathic central precocious puberty (ICPP) is poorly understood. Overall, the genetic modulation of pubertal onset most likely arises from the additive effect of multiple genes, but also monogenic causes of ICPP probably exist, as cases of familial ICPP have been reported. Mutations in KISS1 and KISSR, coding for kisspeptin and its receptor, involved in GnRH secretion and puberty onset, have been suggested causative for monogenic ICPP. Variation in LIN28B was associated with timing of puberty in genome-wide association (GWA) studies. LIN28B is a human ortholog of the gene that controls, through microRNAs, developmental timing in C. elegans. In addition, Lin28a transgenic mice manifest the puberty phenotypes identified in the human GWAS. Thus, both LIN28B and LIN28A may have a role in pubertal development and are good candidate genes for monogenic ICPP. Methods Thirty girls with ICPP were included in the study. ICPP was defined by pubertal onset before 8 yrs of age, and a pubertal LH response to GnRH testing. The coding regions of LIN28B, LIN28A, KISS1, and KISS1R were sequenced. The missense change in LIN28B was also screened in 132 control subjects. Results No rare variants were detected in KISS1 or KISS1R in the 30 subjects with ICPP. In LIN28B, one missense change, His199Arg, was found in one subject with ICPP. However, this variant was also detected in one of the 132 controls. No variation in LIN28A was found. Conclusions We did not find any evidence that mutations in LIN28B or LIN28A would underlie ICPP. In addition, we confirmed that mutations in KISS1 and KISS1R are not a common cause for ICPP.

Monetary policy rules and estimated reaction functions for the European Central Bank

This thesis studies the interest-rate policy of the ECB by estimating monetary policy rules using real-time data and central bank forecasts. The aim of the estimations is to try to characterize a decade of common monetary policy and to look at how different models perform at this task.The estimated rules include: contemporary Taylor rules, forward-looking Taylor rules, nonlinearrules and forecast-based rules. The nonlinear models allow for the possibility of zone-like preferences and an asymmetric response to key variables. The models therefore encompass the most popular sub-group of simple models used for policy analysis as well as the more unusual non-linear approach. In addition to the empirical work, this thesis also contains a more general discussion of monetary policy rules mostly from a New Keynesian perspective. This discussion includes an overview of some notable related studies, optimal policy, policy gradualism and several other related subjects. The regression estimations are performed with either least squares or the generalized method of moments depending on the requirements of the estimations. The estimations use data from both the Euro Area Real-Time Database and the central bank forecasts published in ECB Monthly Bulletins. These data sources represent some of the best data that is available for this kind of analysis. The main results of this thesis are that forward-looking behavior appears highly prevalent, but that standard forward-looking Taylor rules offer only ambivalent results with regard to inflation. Nonlinear models are shown to work, but on the other hand do not have a strong rationale over a simpler linear formulation. However, the forecasts appear to be highly useful in characterizing policy and may offer the most accurate depiction of a predominantly forward-looking central bank. In particular the inflation response appears much stronger while the output response becomes highly forward-looking as well.

Adaptive optimal load balancing in a nonhomogeneous multiserver system with a central job scheduler

A model comprising several servers, each equipped with its own queue and with possibly different service speeds, is considered. Each server receives a dedicated arrival stream of jobs; there is also a stream of generic jobs that arrive to a job scheduler and can be individually allocated to any of the servers. It is shown that if the arrival streams are all Poisson and all jobs have the same exponentially distributed service requirements, the probabilistic splitting of the generic stream that minimizes the average job response time is such that it balances the server idle times in a weighted least-squares sense, where the weighting coefficients are related to the service speeds of the servers. The corresponding result holds for nonexponentially distributed service times if the service speeds are all equal. This result is used to develop adaptive quasi-static algorithms for allocating jobs in the generic arrival stream when the load parameters are unknown. The algorithms utilize server idle-time measurements which are sent periodically to the central job scheduler. A model is developed for these measurements, and the result mentioned is used to cast the problem into one of finding a projection of the root of an affine function, when only noisy values of the function can be observed

Nestedness pattern in stream diatom assemblages of central Western Ghats

Community diversity and the population abundance of a particular group of species are controlled by immediate environment, inter-and intra-species interactions, landscape conditions, historical events and evolutionary processes. Nestedness is a measure of order in an ecological system, referring to the order in which the number of species is related to area or other factors. In this study we have studied the nestedness pattern in stream diatom assemblages in 24 stream sites of central Western Ghats, and report 98 taxa from the streams of central Western Ghats region. The communities show highly significant nested pattern. The Mantel test of matrix revealed a strong relationship between species assemblages and environmental conditions at the sites. A significant relationship between species assemblage and environmental condition was observed. Principal component analysis (PCA) indicated that environmental conditions differed markedly across the sampling sites, with the first three components explaining 78% of variance. Species composition of diatoms is significantly correlated with environmental distance across geographical extent. The current pattern suggests that micro-environment at regional levels influences the species composition of epilithic diatoms in streams. The nestedness shown by the diatom community was highly significant, even though it had a high proportion of idiosyncratic species, characterized with high numbers of cosmopolitan species, whereas the nested species were dominated by endemic species. PCA identifies ionic parameters and nutrients as the major features which determine the characteristics of the sampling sites. Hence the local water quality parameters are the major factors in deciding the diatom species assemblages.

Central Limit Theorem for truncated heavy tailed Banach valued random vectors

In this paper the question of the extent to which truncated heavy tailed random vectors, taking values in a Banach space, retain the characteristic features of heavy tailed random vectors, is answered from the point of view of the central limit theorem.

The central region of meso-3,4-diphenylhexane-2,5-dione

As with 1,2-diphenylethane (dpe), X-ray crystallographic methods measure the central bond in meso-3,4-diphenylhexane-2,5-done (dphd) as significantly shorter than normal for an sp(3)-sp(3) bond. The same methods measure the benzylic (ethane C-Ph) bonds in dphd as unusually long for sp(3)-sp(2) liaisons. Torsional motions of the phenyl rings about the C-Ph bonds have been proposed as the artifacts behind the result of a 'short' central bond in dpe. While a similar explanation can, presumably, hold for the even 'shorter' central bond in dphd, it cannot account for the 'long' C-Ph bonds. The phenyl groups, departing much from regular hexagonal shape, adopt highly skewed conformations with respect to the plane constituted by the four central atoms. It is thought that-the thermal motions of the phenyl rings, conditioned by the potential wells in which they are ensconced in the unit cell, are largely libratory around their normal axes. In what appears to be a straightforward explanation under the 'rigid-body' concept, it appears that these libratory motions of the phenyl rings, that account, at the same time, for the 'short' central bond, are the artifacts behind the 'long' measurement of the C-Ph bonds. These motions could be superimposed on torsional motions analogous to those proposed in the case of dpe. An inspection of the ORTEP diagram from the 298 K data on dphd clearly suggests these possibilities. Supportive evidence for these qualitative explanations from an analysis of the differences between the mean square displacements of C(1) and C(7)/C(1a) and C(7a) based on the 'rigid-body model' is discussed. (C) 2002 Elsevier Science B.V. All rights reserved.

Landslide susceptibility mapping in the downstream region of Sharavathi river basin, Central Western Ghats

Landslides are hazards encountered during monsoon in undulating terrains of Western Ghats causing geomorphic make over of earth surface resulting in significant damages to life and property. An attempt is made in this paper to identify landslides susceptibility regions in the Sharavathi river basin downstream using frequency ratio method based on the field investigations during July- November 2007. In this regard, base layers of spatial data such as topography, land cover, geology and soil were considered. This is supplemented with the field investigations of landslides. Factors that influence landslide were extracted from the spatial database. The probabilistic model -frequency ratio is computed based on these factors. Landslide susceptibility indices were computed and grouped into five classes. Validation of LHS, showed an accuracy of 89% as 25 of the 28 regions tallied with the field condition of highly vulnerable landslide regions. The landslide susceptible map generated for the downstream would be useful for the district officials to implement appropriate mitigation measures to reduce hazards.