Ferroelectricity in DTAAP

The results of dielectric studies of deuterated TAAP grown at different temperatures are reported. These results together with the Raman spectral data show that 100% deuteration is possible only if the crystals are grown at low temperatures. The transition temperature continuously increases with increasing deuterium content from 45°C for TAAP to ∼ 87°C for DTAAP indicating that hydrogen bonds play an important role in the ferroelectric transition of this crystal.

Reducibility of Ce1-xZrxO2: origin of enhanced oxygen storage capacity

We combine first-principles calculations with EXAFS studies to investigate the origin of high oxygen storage capacity in ceria-zirconia solid solution, prepared by solution combustion method. We find that nanocrystalline Ce0.5Zr0.5O2 can be reduced to Ce0.5Zr0.5O1.57 by H-2 upto 850 degrees C with an OSC of 65 cc/gm which is extremely high. Calculated local atomic-scale structure reveals the presence of long and short bonds resulting in four-fold coordination of the cations, confirmed by the EXAFS studies. Bond valence analysis of the microscopic structure and energetics is used to evaluate the strength of binding of different oxide ions and vacancies. We find the presence of strongly and weakly bound oxygens, of which the latter are responsible for the higher oxygen storage capacity in the mixed oxides than in the pure CeO2.

Biosorption of iron(III) from aqueous solutions using the husk of Cicer arientinum

Iron is a major pollutant released as a by-product during several industrial operations especially during acid mining of metal ores. In this paper, the use of Bengal gram husk (husk of channa dal, Cicer arientinum) in the biosorption of Fe(III) from aqueous solutions is discussed. Parameters like agitation time, adsorbent dosage and pH were studied at different Fe(Ill) concentrations. The adsorption data fit well with Langmuir and Freundlich isotherm models. The adsorption capacity (q(max)) calculated from the Langmuir isotherm was 72.16 mg of Fe(III)/g of the biosorbent at an initial pH of 2.5. Desorption Studies were performed at different concentrations of hydrochloric acid showing that quantitative recovery of the metal ion is possible. The infrared spectra of the biomass before and after treatment with Fe(III), revealed that hydroxyl, carboxyl and amide bonds are involved in the uptake of Fe(III) ions.

Keskeytyksiä elämässä : Naisten toimijuudet aborttikertomuksissa

The present study focuses on the question of agency in the narratives of women who have experienced an abortion. The study scrutinizes agency by analyzing narratives and their context, that is, how narratives are entwined with cultural discourses and societal practices. The study thus addresses also the wider framework within which experiences and actions can be constructed in abortion narratives in the contemporary Finnish society. The women who wrote their stories or were interviewed were of different ages and had different social and religious backgrounds. Many variations of agency were found when abortion experiences were analyzed through the women s embodied and historically specific accounts. Independent and rational choices are entwined with emotions and choices made together with other people. Intimate relationships with family and friends have an important role in the choices regarding abortion. These relationships do not, however, simply belong in the private sphere but reflect the wider socio-cultural meanings of social bonds and family ties. Women s agency with regard to abortion is also constructed in encounters with the medical profession and within the wider framework of abortion legislation. The Finnish legislation grants women an abortion within certain parameters but not solely on the basis of a woman s wish to have an abortion. The data consists primarily of written narratives and interviews. All together 39 women shared their experiences with the researcher. The analysis focuses on decision-making regarding abortion, depictions of freedom and responsibility, emotions around abortion and expressions of values and religious views. The links between the women's experiences and the wider socio-cultural norms and institutions are analyzed through materials consisting of public debate on abortion in the media, ethical statements as well as literature and legislation on abortion. The analysis sheds light on the tensions apparent in the women's narratives between the legal status of abortion and more traditional views on abortion. The study demonstrates that the freedom linked to abortion is not solely to do with the right to have an abortion but also how abortion can be experienced, understood and where one can talk about the experience afterwards. The analysis reveals that Christian values shape women's experiences but that there are also new religious ways to deal with the ethical considerations brought about by abortion. Annually over 10 000 Finnish women experience an abortion, which is a situation involving ethical considerations. The study provides a nuanced account of the ways in which one can think and act when going through an abortion.

Crystal structure and conformation study of N-methyl-t-3-methyl-r-2, c-6-diphenylpiperidin-4-one thiosemicarbazone

Thiosemicarbazones are having the ability to bind with metal and inhibit the enzyme ribonucleoside diphosphate reductase(RDR),an enzyme which is involved in the synthesis of DNA precursors in the mammalian cells.The title compound N-methyl-t-3-methyl-r-2, c-6-diphenylpiperidin-4-one thiosemicarbazone (NMMDPT), CCDC 218052, was prepared using Mannich reaction and characterized by X-ray diffraction methods.The crystal data are:C20H24N4S; M.W= 352.49, triclinic,space group P (1) over bar, a = 8.467(2)angstrom, b = 10.228(2)angstrom, c = 12.249(2)angstrom; lpha=92.595(3)degrees, beta=104.173(3)degrees, gamma=13.628(3)degrees; V=930.0(3)angstrom(3), Z=2, D-cal=1.259Mgm(-3),mu=0.184mm(-1),lambda (MoKalpha)=0.71073 angstrom, final R1 and wR2 are 0.0470 and 0.1052, respectively. The piperidine rings adopt chair conformation. The planar phenyl rings are oriented equatorially at 2,6-positions of the piperidine ring. The molecular packing can be viewed as dimers held together by two N-H...S types of intermolecular hydrogen bonds. Weak C-H...pi interactions also support the stability of the molecules in the crystal in addition to van der Waals forces. (c) 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Correlation between stick-slip frictional sliding and charge transfer

A decade ago, Budakian and Putterman [Phys. Rev. Lett. 85, 1000 (2000)] ascribed friction to the formation of bonds arising from contact charging when a gold tip of a surface force apparatus was dragged on polymethylmethacrylate surface. We propose a stick-slip model that captures the observed correlation between stick-slip events and charge transfer, and the lack of dependence of the scale factor connecting the force jumps and charge transfer on normal load. Here, stick-slip dynamics arises as a competition between the viscoelastic and plastic deformation time scales and that due to the pull speed with contact charging playing a minor role. Our model provides an alternate basis for explaining most experimental results without ascribing friction to contact charging.

Molecular Complexes of Alprazolam with Carboxylic Acids, Boric Acid, Boronic Acids, and Phenols. Evaluation of Supramolecular Heterosynthons Mediated by a Triazole Ring

A series of molecular complexes, both co-crystals and salts, of a triazole drug-alprazolam-with carboxylic acids, boric acid, boronic acids, and phenols have been analyzed with respect to heterosynthons present in the crystal structures. In all cases, the triazole ring behaves as an efficient hydrogen bond acceptor with the acidic coformers. The hydrogen bond patterns exhibited with aromatic carboxylic acids were found to depend on the nature and position of the substituents. Being a strong acid, 2,6-dihydroxybenzoic acid forms a salt with alprazolam. With aliphatic dicarboxylic acids alprazolam forms hydrates and the water molecules play a central role in synthon formation and crystal packing. The triazole ring makes two distinct heterosynthons in the molecular complex with boric acid. Boronic acids and phenols form consistent hydrogen bond patterns, and these are seemingly independent of the substitutional effects. Boronic acids form noncentrosymmetric cyclic synthons, while phenols form O-H center dot center dot center dot N hydrogen bonds with the triazole ring. (C) 2010 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 99:3743-3753, 2010.

Photo induced optical changes in Sb/As2S3 multilayered film and (As2S3)(0.93)Sb-0.07 film of equal thickness

The increase in optical band gap (photo bleaching) due to light illumination was studied at room temperature as well as at low (4.2 K) temperature for Sb/As2S3 multilayered film of 640 nm thickness by Fourier Transform Infrared Technique. The interdiffusion of Sb into As2S3 matrix results the formation of Sb-As2S3 ternary solid solutions which is explained by the change in optical band gap (E-g), absorption coefficient (alpha), Tauc parameter (B-1/2), Urbach edge (E-e). At the same time, photo darkening phenomena was observed in (As2S3)(0.93)Sb-0.07 film of same thickness both at low and room temperatures. From our X-ray Photoelectron Spectroscopy measurements,we are able to show that some of the As-As, S-S and Sb-Sb bonds are converted into As-S and S-Sb bonds in case of multilayers. We found that the energetically favoured heteropolar bond formation take place by a phonon-assisted mechanism using the lone pair pi electrons of S-2(0). But in case of (As2S3)(0.93)Sb-0.02 film, the homopolar bonds are playing a major role. (C) 2010 Elsevier B.V. All rights reserved.

Conformational analysis of the right-hand twisted antiparallel β-Structure

The conformational analysis of a pair of two-linked peptide units in the anti-parallel arrangement is reported here with a view to study the effect of association of one chain with the other. The pair of two-linked peptide units were fixed in space through the hydrogen bonds between them, in accordance with certain hydrogen bond criteria. Model building was undertaken to ascertain whether the proximity of the side-chains could be used to eliminate any one of the right-hand twisted, left-hand twisted or regular β-structures. Stereochemically, it was found possible with all of them. The preference for a right-hand twisted β-structure, however, was indicated by the classical energy calculations. The relevance of the results thus obtained is discussed in the context of the preferential right-hand twist of the β-pleated sheets present in globular proteins. The agreement between the minimum energy conformations obtained for the pair of two-linked peptide units and the globular protein data is also indicated.

Studies on the phase transitions in thiourea

Thiourea (CS(NH2)2) is one of the few examples of molecular crystals exhibiting ferroelectric properties. The dielectric constant along the ferroelectric axis [100] shows maxima at 169, 177 and 202 K. An inflection point occurs at 170.5 KZ Following Goldsmith and White the phases are named as I (F.E. below 169 K), II (A.F.E. 169 Kbonds.

Proteolytic susceptibility and methionine modification of monodeamidated ribonuclease A

The susceptibility of a monodeamidated RNAaseA (RNAaseAa1) towards carboxypeptidaseA , alpha-chymotrypsin and pepsin has been studied. Similar to RNAaseA, the C-terminal of RNAaseAa1 is not available for carboxypeptidaseA hydrolysis. The thermal stability of RNAaseAa1 as probed through chymotryptic digestion is found to be less than that of RNAaseA. Preliminary chromatographic analysis of the digested material, however, suggests that the nature of thermal transition might be the same in the two proteins. Pepsin inactivates RNAaseAa1 more slowly than does RNAaseA. Accordingly, less peptide bonds, almost half that of RNAaseA, are cleaved by pepsin in RNAaseAa1. The accumulation of RNAase-P type intermediates is not evident during peptic digestion of RNAaseAa1. Reaction with O-benzoquinone at low pH shows that methionines of the deamidated protein seem to have higher reactivities. These observations indicate a different structure for RNAaseAa1 at elevated temperature and low pH.

Discovery of oxidative enzymes for food engineering : Tyrosinase and sulfhydryl oxidase

Enzymes offer many advantages in industrial processes, such as high specificity, mild treatment conditions and low energy requirements. Therefore, the industry has exploited them in many sectors including food processing. Enzymes can modify food properties by acting on small molecules or on polymers such as carbohydrates or proteins. Crosslinking enzymes such as tyrosinases and sulfhydryl oxidases catalyse the formation of novel covalent bonds between specific residues in proteins and/or peptides, thus forming or modifying the protein network of food. In this study, novel secreted fungal proteins with sequence features typical of tyrosinases and sulfhydryl oxidases were iden-tified through a genome mining study. Representatives of both of these enzyme families were selected for heterologous produc-tion in the filamentous fungus Trichoderma reesei and biochemical characterisation. Firstly, a novel family of putative tyrosinases carrying a shorter sequence than the previously characterised tyrosinases was discovered. These proteins lacked the whole linker and C-terminal domain that possibly play a role in cofactor incorporation, folding or protein activity. One of these proteins, AoCO4 from Aspergillus oryzae, was produced in T. reesei with a production level of about 1.5 g/l. The enzyme AoCO4 was correctly folded and bound the copper cofactors with a type-3 copper centre. However, the enzyme had only a low level of activity with the phenolic substrates tested. Highest activity was obtained with 4-tert-butylcatechol. Since tyrosine was not a substrate for AoCO4, the enzyme was classified as catechol oxidase. Secondly, the genome analysis for secreted proteins with sequence features typical of flavin-dependent sulfhydryl oxidases pinpointed two previously uncharacterised proteins AoSOX1 and AoSOX2 from A. oryzae. These two novel sulfhydryl oxidases were produced in T. reesei with production levels of 70 and 180 mg/l, respectively, in shake flask cultivations. AoSOX1 and AoSOX2 were FAD-dependent enzymes with a dimeric tertiary structure and they both showed activity on small sulfhydryl compounds such as glutathione and dithiothreitol, and were drastically inhibited by zinc sulphate. AoSOX2 showed good stabil-ity to thermal and chemical denaturation, being superior to AoSOX1 in this respect. Thirdly, the suitability of AoSOX1 as a possible baking improver was elucidated. The effect of AoSOX1, alone and in combi-nation with the widely used improver ascorbic acid was tested on yeasted wheat dough, both fresh and frozen, and on fresh water-flour dough. In all cases, AoSOX1 had no effect on the fermentation properties of fresh yeasted dough. AoSOX1 nega-tively affected the fermentation properties of frozen doughs and accelerated the damaging effects of the frozen storage, i.e. giving a softer dough with poorer gas retention abilities than the control. In combination with ascorbic acid, AoSOX1 gave harder doughs. In accordance, rheological studies in yeast-free dough showed that the presence of only AoSOX1 resulted in weaker and more extensible dough whereas a dough with opposite properties was obtained if ascorbic acid was also used. Doughs containing ascorbic acid and increasing amounts of AoSOX1 were harder in a dose-dependent manner. Sulfhydryl oxidase AoSOX1 had an enhancing effect on the dough hardening mechanism of ascorbic acid. This was ascribed mainly to the produc-tion of hydrogen peroxide in the SOX reaction which is able to convert the ascorbic acid to the actual improver dehydroascorbic acid. In addition, AoSOX1 could possibly oxidise the free glutathione in the dough and thus prevent the loss of dough strength caused by the spontaneous reduction of the disulfide bonds constituting the dough protein network. Sulfhydryl oxidase AoSOX1 is therefore able to enhance the action of ascorbic acid in wheat dough and could potentially be applied in wheat dough baking.

“Aivan sama vaikkei ne olis edes pelannut” – Jalkapallo elämyskulutuksen kohteena

Tutkielmassa tarkastellaan jalkapallon seuraamista elämyskuluttamisen näkökulmasta. Elämyskulutuksella tarkoitetaan tässä yhteydessä tapahtumia ja hetkiä, jolloin ihminen kokee tavallisuudesta poikkeavan ja mieleenpainuvan tunnetilan. Elämyksiä tarjoavat palvelut ovat lisänneet jatkuvasti suosiotaan, kun arjessa rationaalisuus ylikorostuu ja sille halutaan vastapainoa. Aihetta taustoitetaan elämysyhteiskunnan, yhteisöllisyyden ja kuluttajaheimojen käsitteiden avulla. Erityishuomion saavat kulttuuritapahtumat elämystuotteina, penkkiurheilu yhteiskunnallisena ilmiönä sekä erilaiset jalkapalloon liittyvät kulutustavat. Tutkielma on luonteeltaan fenomenologis-etnografinen kuvaileva tutkimus. Tutkimusmenetelminä on käytetty osallistuvaa havainnointia ja haastatteluita. Tutkimusperinteen mukaisesti ilmiön ymmärtäminen, kuvaaminen ja kirjoittaminen ovat tärkeässä osassa. Havainnointiaineisto on kerätty kolmessa eri tapahtumassa seuraamalla katsojien käyttäytymistä ja tunnelman syntymiseen vaikuttavia tekijöitä. Haastateltavat on valittu harkinnanvaraisesti jalkapalloa aktiivisesti seuraavista henkilöistä ja menetelmänä on käytetty avoimia teemahaastatteluita. Urheilun vetovoima ajanvietteenä perustuu vahvojen tunteiden herättämiseen, joten penkkiurheilu on elämyskulutusta puhtaimmillaan. Urheilu elämystuotteena on oivallinen, sillä sen lukuisten kulutustapojen lisäksi tapahtumat muodostavat päättymättömän jatkumon. Myös oman aineistoni perusteella osoittautui, että menneiden tapahtumien avulla ankkuroidutaan yhteisöön ja tulevien tapahtumien avulla pidetään innostusta yllä. Pettymysten hetkelläkään koukusta ei haluta irti, sillä jokainen kokemus lisää tunteita omaa urheilulajia ja yhteisöä kohtaan. Urheilutapahtumissa katsojan elämys syntyy subjektiivisen kokemuksen kautta, mutta yhteisö luo elämyksen toteutumisen välttämättömät edellytykset. Jalkapalloyleisöön kuuluvissa henkilöissä yhdistyvät halu kuulua ryhmään ja olla samaan aikaan sen ulkopuolella. Peliä voidaan tarkkailla itsekseen ja keskittyneesti suuren joukon keskellä tai hurrata muiden mukana. Aineistoni perusteella jalkapallofanin innostus pulppuaa kahdesta lähteestä: yhteisöllisyydestä ja kiinnostuksesta lajiin. Yhteisöllisyyden tunne syntyy kuulumisesta globaaliin jalkapalloyhteisöön, oman suosikkijoukkueen kannattajiin ja samaa lajia seuraavien kaverien muodostamaan lähipiiriin. Urheilullinen puoli innostuksesta syntyy kiinnostuksesta jalkapalloa kohtaan lajina, aktiivisesti seuratuista säännöllisistä tapahtumista ja oman joukkueen kannattamisesta. Jalkapallon seuraajiin teoria jatkuvasti muuttuvista uusyhteisöistä pätee melko huonosti, sillä lajille ja seuralle ollaan hyvin uskollisia. Faneille on tärkeää sitoutua pieneen lähiyhteisöön, jonka kanssa heillä on yhteinen historia ja mahdollisuus jakaa kokemuksia keskustelemalla ja muistelemalla.

Stabilization of the bio-membrane by small molecules: interaction of trehalose with the phospholipid bilayer

Anhydrobiotic organisms undergo periods of acute dehydration during their life cycle. It is of interest to understand how the biomembrane remains intact through such stress. A disaccharide, trehalose, which is metabolised during anhydrobiosis is found to prevent disruption of model membrane systems. Molecular modelling techniques are used to investigate the possible mode of interaction of trehalose with a model monolayer. The objective is to maximise hydrogen bonding between the two systems. A phospholipid matrix consisting of 1,2-dimyristoyl-sn-glycero-3-phosphatidylcholine (DMPC) is chosen to represent the monolayer. The crystal structure of DMPC reveals that there are two distinct conformers designated as A and B. An expansion of the monolayer, coplanar with its surface, results in the trehalose molecule being accommodated in a pocket formed by four B conformers. One glucose ring of the sugar rests on the hydrophobic patch provided by the choline methyls of an A conformer. Five hydrogen bonds are formed involving the phosphate oxygens of three of the surrounding B conformers. The model will be discussed with reference to relevant experimental data on the interaction.

Stereochemistry of collagen

This review article, based on a lecture delivered in Madras in 1985, is an account of the author's experience in the working out of the molecular structure and conformation of the collagen triple-helix over the years 1952–78. It starts with the first proposal of the correct triple-helix in 1954, but with three residues per turn, which was later refined in 1955 into a coiled-coil structure with approximately 3.3 residues per turn. The structure readily fitted proline and hydroxyproline residues and required glycine as every third residue in each of the three chains. The controversy regarding the number of hydrogen bonds per tripeptide could not be resolved by X-ray diffraction or energy minimization, but physicochemical data, obtained in other laboratories during 1961–65, strongly pointed to two hydrogen bonds, as suggested by the author. However, it was felt that the structure with one straight NH … O bond was better. A reconciliation of the two was obtained in Chicago in 1968, by showing that the second hydrogen bond is via a water molecule, which makes it weaker, as found in the physicochemical studies mentioned above. This water molecule was also shown, in 1973, to take part in further cross-linking hydrogen bonds with the OH group of hydroxyproline, which occurred always in the location previous to glycine, and is at the right distance from the water. Thus, almost all features of the primary structure, X-ray pattern, optical and hydrodynamic data, and the role of hydroxyproline in stabilising the triple helical structure, have been satisfactorily accounted for. These also lead to a confirmation of Pauling's theory that vitamin C improves immunity to diseases, as explained in the last section.