Bond length distortions associated with torsion potentials; ab-initio studies on methanedio

The 4-31G basis set is used to study the bond length variations as functions of dihedral angels in methanediol. This study is compared with O---C---O bond angle optimization studies by Gorenstein and Kar and the possible reason for bond length shorteing in the trans---trans configuration is analysed.

Molecular conformation of alamethicin in dimethylsulfoxide solution A two-dimensional n.m.r. study

The solution conformation of alamethicin, a 20-residue antibiotic peptide, has been investigated using two-dimensional n.m.r. spectroscopy. Complete proton resonance assignments of this peptide have been carried out using COSY, SUPERCOSY, RELAY COSY and NOESY two-dimensional spectroscopies. Observation of a large number of nuclear Overhauser effects between sequential backbone amide protons, between backbone amide protons and CβH protons of preceding residues and extensive intramolecular hydrogen bonding patterns of NH protons has established that this polypeptide is in a largely helical conformation. This result is in conformity with earlier reported solid state X-ray results and a recent n.m.r. study in methanol solution (Esposito et al. (1987) Biochemistry26, 1043-1050) but is at variance with an earlier study which favored an extended conformation for the C-terminal half of alamethicin (Bannerjee et al.

Spectral Invariance of SG Pseudo-Differential Operators on L-P(R-n)

We prove the spectral invariance of SG pseudo-differential operators on L-P(R-n), 1 < p < infinity, by using the equivalence of ellipticity and Fredholmness of SG pseudo-differential operators on L-p(R-n), 1 < p < infinity. A key ingredient in the proof is the spectral invariance of SC pseudo-differential operators on L-2(R-n).

Aqueous channels within apolar peptide aggregates. Solvated helix of Boc-Aib-Ala-Leu-Aib-Ala-Leu-Aib- -Ala-Leu-Aib-OMe. H2O.CH3OH

Although the peptide Boc-Aibl-Ala2-Leu3- Aib4-Alas Leu'-Aib7-Ala8-Leu9-Aib'0-OMe [with a t-butoxycarbonyl(Boc) blocking group at the amino terminus, a methyl ester (OMe) at the carboxyl terminus, and four a-aminoisobutyric (Aib) residues] has a 3-fold repeat of residues, the helix formed by the peptide backbone is irregular. The carboxyl-terminal half assumes an at-helical form with torsion angles ) and r of approximately -60° and -45°, respectively, whereas the amino-terminal half is distorted by an insertion of a water molecule between the amide nitrogen of Ala5 [N(5)] and the carbonyl oxygen of Ala2 [0(2)]. The water molecule W(1) acts as a bridge by forming hydrogen bonds N(5).W(1) (2.93 A) and W(1)---0(2) (2.86 A). The distortion of the helix exposes the carbonyl oxygens of Aib' and Aib4 to the outside environment, with the consequence that the helix assumes an amphiphilic character despite having all apolar residues. Neighboring helices in the crystal run in antiparallel directions. On one side of a helix there are only hydrophobic contacts with efficient interdigitation of leucine side chains with those from the neighboring helix. On the other side of the helix there are hydrogen bonds between protruding carbonyl oxygens and four water molecules that separate two neighboring helices. Along the helix axis the helices bind head-to-tail with a direct hydrogen bond N(2)-0(9) (3.00 A). Crystals grown from methanol/water solution are in space group P2, with a = 15.778 ± 0.004 A, b = 11.228 ± 0.002 A, c = 18.415 ± 0.003 A, = 102.10 ± 0.02ur and two formula units per cell for C49HON1003 2H2OCH3OH. The overall agreement factorR is 7.5% for 3394 reflections observed with intensities >3a(F), and the resolution is 0.90 A.

Correlation of helicopter rotor aeroelastic response with HART-II wind tunnel test data

Purpose - This paper aims to validate a comprehensive aeroelastic analysis for a helicopter rotor with the higher harmonic control aeroacoustic rotor test (HART-II) wind tunnel test data. Design/methodology/approach - Aeroelastic analysis of helicopter rotor with elastic blades based on finite element method in space and time and capable of considering higher harmonic control inputs is carried out. Moderate deflection and coriolis nonlinearities are included in the analysis. The rotor aerodynamics are represented using free wake and unsteady aerodynamic models. Findings - Good correlation between analysis and HART-II wind tunnel test data is obtained for blade natural frequencies across a range of rotating speeds. The basic physics of the blade mode shapes are also well captured. In particular, the fundamental flap, lag and torsion modes compare very well. The blade response compares well with HART-II result and other high-fidelity aeroelastic code predictions for flap and torsion mode. For the lead-lag response, the present analysis prediction is somewhat better than other aeroelastic analyses. Research limitations/implications - Predicted blade response trend with higher harmonic pitch control agreed well with the wind tunnel test data, but usually contained a constant offset in the mean values of lead-lag and elastic torsion response. Improvements in the modeling of the aerodynamic environment around the rotor can help reduce this gap between the experimental and numerical results. Practical implications - Correlation of predicted aeroelastic response with wind tunnel test data is a vital step towards validating any helicopter aeroelastic analysis. Such efforts lend confidence in using the numerical analysis to understand the actual physical behavior of the helicopter system. Also, validated numerical analyses can take the place of time-consuming and expensive wind tunnel tests during the initial stage of the design process. Originality/value - While the basic physics appears to be well captured by the aeroelastic analysis, there is need for improvement in the aerodynamic modeling which appears to be the source of the gap between numerical predictions and HART-II wind tunnel experiments.

Biochemical, histopathological and ultrastructural changes in rat liver induced by r-( + )-pulegone, a monoterpene ketone

Biochemical, histopathological and ultrastructural changes occurring at different time points after intraperitoneal administration of a single dose of pulegone (300 mg/kg) were studied. Significant decreases in the level of liver microsomal cytochrome P-450 (67%), heme (37%), aminopyrine N-demethylase (60%) and glucose-6-phosphatase (58%), were noticed 24 hr after pulegone treatment. Alanine amino transferase (ALT) levels increased in a time dependent manner, following exposure of rats to pulegone. Light microscopic studies of liver tissues showed dilation of central veins and distention of sinusoidal spaces 6 hr after pulegone treatment. Initial centrilobular necrosis was noticed at 12 hr. Centrilobular necrosis became severe at 18 hr and nuclear changes included karyorrhexis and karyolysis. Midzonal and periportal degenerative changes in addition to centrilobular necrosis was observed 24 hr after pulegone administration. Electron microscopic changes showed severe degeneration of endoplasmic reticulum, swelling of mitochondria and nuclear changes, 24 hr after administration of pulegone. The time course profile of the hepatocytes after treatment with pulegone indicates that endoplasmic reticulum is the organelle most affected, following which other degenerative changes occur ultimately leading to cell death.

Inelastic dynamic response of R.C. beam column joints by using B.E.M.

A BEM formulation to obtain the inelastic response of R.C. Beam-Column joints subjected to sinusoidal loading along the boundary is presented. The equations of motion are written along with kinematical and constitutive equations. The dynamic reciprocal theorem is presented and the temporal dependence is removed by assuming steady state response.

Polyquinanes from (R)-(+)-limonene. Enantioselective total synthesis of the novel tricyclic sesquiterpene (-)-ceratopicanol

The first total synthesis of the biogenetically important and structurally novel triquinane sesquiterpene (-)-ceratopicanol has been accomplished.

Visualisation of a 2′-5′ parallel stranded double helix at atomic resolution: crystal structure of cytidylyl-2′,5′-adenosine

X-ray crystallographlc studies on 3′–5′ ollgomers have provided a great deal of information on the stereochemistry and conformational flexibility of nucleic acids and polynucleotides. In contrast, there is very little Information available on 2′–5′ polynucleotides. We have now obtained the crystal structure of Cytidylyl-2′,5′-Adenoslne (C2′p5′A) at atomic resolution to establish the conformational differences between these two classes of polymers. The dlnucleoside phosphate crystallises in the monocllnlc space group C2, with a = 33.912(4)Å, b =16.824(4)Å, c = 12.898(2)Å and 0 = 112.35(1) with two molecules in the asymmetric unit. Spectacularly, the two independent C2′p5′A molecules in the asymmetric unit form right handed miniature parallel stranded double helices with their respective crystallographic two fold (b axis) symmetry mates. Remarkably, the two mini duplexes are almost indistinguishable. The cytosines and adenines form self-pairs with three and two hydrogen bonds respectively. The conformation of the C and A residues about the glycosyl bond is anti same as in the 3′–5′ analog but contrasts the anti and syn geometry of C and A residues in A2′p5′C. The furanose ring conformation is C3′endo, C2′endo mixed puckering as in the C3′p5′A-proflavine complex. A comparison of the backbone torsion angles with other 2′–5′ dinucleoside structures reveals that the major deviations occur in the torsion angles about the C3′–C2′ and C4′-C3′ bonds. A right-handed 2′–5′ parallel stranded double helix having eight base pairs per turn and 45° turn angle between them has been constructed using this dinucleoside phosphate as repeat unit. A discussion on 2′–5′ parallel stranded double helix and its relevance to biological systems is presented.

Otoksen edustavuuden mittaus R-indikaattorin avulla Suomen uhritutkimuspilotissa

Tutkielmassa sovelletaan aineiston edustavuutta mittaavaa laatuindikaattoria Suomen uhritutkimuspilottiin tilanteessa, jossa ilmenee vastauskatoa. Vastauskato on kasvava ongelma tilastotutkimuksissa: jos tutkimukseen osallistuneet eivät edusta otosjoukkoa tutkittavan asian suhteen, voi vastauskadosta aiheutuva harha olla estimoiduissa tunnusluvuissa hyvinkin suuri. Tutkimuksissa näkee usein julkaistavan vastausasteen ikään kuin se kertoisi aukottomasti tutkimuksen laadusta. Pelkkä korkea vastausaste ei kuitenkaan välttämättä takaa estimaattien harhattomuutta, sillä se ei kerro mitään vastanneiden ja vastaamattomien eroista tutkittavan asian suhteen. Tarvitaan siis muita mittareita, joilla vastanneiden laatua voitaisiin paremmin arvioida, ja R-indikaattori tarjoaa yhden vaihtoehdon. R-indikaattori mittaa otosalkioiden vastausalttiuksien välistä vaihtelua. R-indikaattorin estimoiminen edellyttää siis vastausalttiuksien estimointia, mikä puolestaan edellyttää apumuuttujien olemassaoloa kaikille otosalkioille. Vastausalttiuksien estimoimiseen käytettiin linkkifunktiona sekä logistista mallia että ja Särndalin ja Lundströmin (2008) vastausvaikutusten mallia. Vastauskäyttäytymiseen vaikuttavan apumuuttujajoukon valinta tehtiin alan kirjallisuuteen perustuen (Groves & Couper 1998). Koska R-indikaattorin estimaattori on satunnaismuuttuja, täytyi sille estimoida varianssi ja mahdollinen harha (Shlomo ym. 2009). Estimoinnissa käytettiin Bootstrap-pseudotoistomenetelmää, jossa alkuperäisestä aineistosta poimitaan niin kutsuttuja pseudo-otoksia, joiden avulla R-indikaattorin estimaattorille voidaan laskea keskivirhe. Suomen uhritutkimuspilotti koostui kolmesta eri tiedonkeruumenetelmällä poimitusta otoksesta: CAPI-, CATI- CAVVIotoksesta. Vastausasteet vaihtelivat aineistoissa paljon, mutta R-indikaattorin estimaatit olivat kaikille aineistoille liki samat. Suurempi vastausaste ei siis merkinnyt parempaa edustavuutta. Lisäksi CAVVI-aineistossa muistutusviestein ja -kirjein suoritettu vastausasteen kasvattaminen huononsi edustavuutta R-indikaattorin näkökulmasta. Mielivaltainen vastausasteen kasvattaminen ei siis ole välttämättä perusteltua. R-indikaattorin estimaattorin ominaisuuksien osalta empiiriset tulokset vahvistivat RISQ-projektin aiempia tutkimustuloksia. Estimaattorin arvo oli sitä pienempi mitä enemmän vastausalttiuden mallissa oli selittäjiä, koska tällöin vastausalttiuksien varianssi kasvoi (Schouten ym. 2009). Otoskoko vaikutti merkittävästi varianssin suuruuteen: mitä pienempi otoskoko oli, sitä leveämmät olivat luottamusvälit ja sitä vaikeampi oli tehdä johtopäätöksiä edustavuudesta.