Conformation of the flexible bent helix of Leu1-zervamicin in crystal C and a possible gating action for ion passage

The membrane channel-forming polypeptide, Leu(1)-zervamicin, Ac-Leu-Ile-Gln-Iva-Ile(5)-Thr-Aib-Leu-Aib-Hyp(10) -Gln-Aib-Hyp-Aib-Pro(15)-Phol (Aib: alpha-aminoisobutyric acid; Iva: isovaline; Hyp: 4-hydroxyproline; Phol: phenylalininol) has been analyzed by x-ray diffraction in a third crystal form. Although the bent helix is quite similar to the conformations found in crystals A and B, the amount of bending is more severe with a bending angle approximate to 47 degrees, The water channel formed by the convex polar faces of neighboring helices is larger at the mouth than in crystals A and B, and the water sites have become disordered. The channel is interrupted in the middle by a hydrogen bond between the OH of Hyp(10) and the NH2 of the Gln(11) of a neighboring molecule. The side chain of Gln(11) is wrapped around the helix backbone in an unusual fashion in order that it can augment the polar side of the helix. In the present crystal C there appears to be an additional conformation for the Gln(11) side chain (with approximate to 20% occupancy) that opens the channel for possible ion passage. Structure parameters for C85H140N18O22.xH(2)O.C2H5OH are space group P2(1)2(1)2(1), a = 10.337 (2) Angstrom, b = 28.387 (7) Angstrom, c = 39.864 (11) Angstrom, Z = 4, agreement factor R = 12.99% for 3250 data observed > 3 sigma(F), resolution = 1.2 Angstrom. (C) 1994 John Wiley & Sons, Inc.

Oral health and menopause

Hormone therapy (HT) is widely used to relieve climacteric symptoms in order to increase the well-being of the women. The benefits as well as side-effects of HT are well documented. The principal menopausal oral symptoms are dry mouth (DM) and sensation of painful mouth (PM) due to various causes. Profile studies have indicated that HT users are more health-conscious than non-users. The hypothesis of the present study was that there are differences in oral health between woman using HT and those not using HT. A questionnaire study of 3173 women of menopausal age (50-58 years old) was done to investigate the prevalence of self-assessed sensations of PM and DM. Of those women participating in the questionnaire study, a random sample of 400 (200 using, 200 not using HT) was examined clinically in a 2-year follow-up study. Oral status was recorded according to WHO methods using DMFT and CPITN indices. The saliva flows were measured, salivary total protein, albumin and immunoglobulin concentrations and selected periodontal micro-organisms were analysed, and panoramic tomography of the jaws was taken. The patients filled in a structured questionnaire on their systemic health, medication and health habits. According to our questionnaire study there was no significant difference in the occurrence of self- assessed PM or DM between the HT users and non-users. According to logistic regression analyses, climacteric complaints significantly correlated with the occurrence of PM (p=0.000) and DM (p=0.000) irrespective of the use of HT, indicating that PM and DM are associated with climacteric symptoms in general. There was no difference between the groups in DMFT index values at follow up. The number of filled teeth (FT) showed a significant (p<0.05) increase in the HT group at follow-up. Periodontitis was diagnosed in 79% of HT users at baseline and in 71% at the follow-up. The values for non-HT users were 80% vs. 76%, respectively (Ns.). The mean numbers of ≥ 6 mm deep periodontal pockets were 0.9 ± 1.7 at baseline vs. 1.1 ± 2.1 two years later in the HT group, and 1.0 ± 1.7 vs. 1.2 ± 1.9, respectively, in the non-HT group. In a large Finnish national health survey, the prevalence of peridontitis of women of this age group was lower, but the prevalence of severe periodontitis seemed to be higher than in our study. Salivary albumin, IgG and IgM concentrations decreased in the HT group during the 2-year follow up (p<0.05), possibly indicating an improvement in epithelial integrity. No difference was found in any other salivary parameters or in the prevalence of the periodontal bacteria between or within the groups. In conclusion, the present findings showed that 50 to 58 year old women living in Helsinki have fairly good oral and dental health. The occurrence of PM and DM seemed to be associated with climacteric symptoms in general, and the use of HT did not affect the oral symptoms studied.

Sex steroids in Sjögren's syndrome

Sjögren s syndrome (SS) is a strongly female dominant autoimmune disease. SS targets mainly salivary and lacrimal glands and leads to loss of the secreting acinar cells of these glands. Accordingly, secretion of the affected glands is diminished and the main symptoms of SS, dryness of mouth and eyes, follow. In addition to these sicca symptoms, SS patients suffer from severe fatigue and can have various extraglandular symptoms. To date, the etiology of SS still remains unknown. Female dominance and the late onset of the disease simultaneously with remarkable hormonal changes in the body (menopause, adrenopause) encouraged us to hypothesize that sex steroids, especially androgens, are involved in the onset and progression of SS. We confirmed our hypothesis and showed that patients with SS suffer from androgen depletion both systemically and locally in the target tissue of SS, salivary glands. We especially focused on the local androgen environment in salivary glands and demonstrated that healthy salivary glands contain a complete enzymatic machinery for local synthesis of androgens and estrogens from pro-hormone dehydroepiandrosterone (DHEA). However, in SS salivary glands the enzymes catalyzing the local androgen synthesis are defective and, in a subgroup of patients, practically non-functional. Probably due to this local defect in DHEA processing, therapy with DHEA was found unbeneficial for SS patients in the treatment of fatigue. We also studied the effect of the local androgen depletion on salivary glands. We found that in salivary gland cells and healthy labial salivary glands androgens upregulate integrin subunits α1 and α2, which are important for the communication, differentiation and function of the acinar cells. On the contrary, in SS salivary glands DHEA failed to upregulate these signaling molecules, again probably due to defective processing of DHEA into active androgens. Our finding highlights the importance of the local androgen environment and local DHEA processing for the function and welfare of salivary glands. In conclusion, this study showed that patients with SS are androgen depleted both systemically and locally in salivary glands. SS patients also have a defective local sex steroid synthesizing enzymatic machinery further impairing the local androgen depletion. We also showed that the local androgen defect leads to decreased expression of acinar cell specific integrin molecules, which impairs the signaling between the acinar cells and basement membrane and might thus explain the acinar cell loss seen in SS salivary glands. By showing the importance of the local sex steroid imbalance in SS we have clarified some etiopathogenetic mechanisms of SS, which have thus far remained unknown.

Genetic characterization of Indian type O FMD virus 3A region in context with host cell preference

The 3A region of foot-and-mouth disease virus has been implicated in host range and virulence. For example, amino acid deletions in the porcinophilic strain (O/TAW/97) at 93-102 aa of the 153 codons long 3A protein have been recognized as the determinant of species specificity. In the present study, 18 type 0 FMDV isolates from India were adapted in different cell culture systems and the 3A sequence was analyzed. These isolates had complete 3A coding sequence (153 aa) and did not exhibit growth restriction in cells based on species of origin. The 3A region was found to be highly conserved at N-terminal half (1-75 aa) but exhibited variability or substitutions towards C-terminal region (80-153). Moreover the amino acid substitutions were more frequent in recent Indian buffalo isolates but none of the Indian isolates showed deletion in 3A protein, which may be the reason for the absence of host specificity in vitro. Further inclusive analysis of 3A region will reveal interesting facts about the variability of FMD virus 3A region in an endemic environment. (C) 2010 Elsevier B.V. All rights reserved.

Informell marknadskommunikation. Teoretisk analys jämte en studie av användningsmöjligheter inom banksektorn

Det är helt naturligt att konsumenterna sprider marknadsinformation genom att sinsemellan prata om sina konsumtionserfarenheter. Även om man i marknadsföringslitteraturen betonar den konsumentdominerade informella marknadskommunikationens genuina karaktär jämfört med den företagsdominerade formella marknadskommunikationen, så har man rätt dåliga kunskaper om företagets möjligheter att systematiskt utnyttja denna typ av marknadskommunikation. Min analys tyder på att den beteendevetenskapliga och den företagsekonomiska word-of-mouth-forskningen anlägger olika perspektiv som inte möter varandra. Den beteendevetenskapliga word-of-mouth-forskningen har tydligare satt fokus på själva företeelsen informell marknadskommunikation, men perspektivet har inte varit speciellt företagsorienterat. Den företagsekonomiska word-of-mouth-forskningen har i sin tur varit betydligt tydligare fokuserad på möjligheterna att använda informell marknadskommunikation, men däremot har man inte fäst speciellt mycket uppmärksamhet vid själva företeelsen informell marknadskommunikation. Min kontribution till den vetenskapliga diskussionen om företagens möjligheter att systematisera utnyttjandet av informell marknadskommunikation består i att överbrygga denna dualism inom word-of-mouth-forskningen genom att anlägga ett företagsperspektiv på den sociala dynamiken för informell marknadskommunikation. Denna ansats har sin teoretiska förankring hos de s.k. moderna men bortglömda pionjärerna, med vilka jag avser Johan Arndt, Donald Cox och Ernest Dichters kontribution till den företagsorienterade word-of-mouth-forskningen redan i slutet av 1960-talet. Efter det har deras synpunkter och insikter varken förts vidare eller vidareutvecklats, vilket jag betraktar som ett bakslag för den företagsorienterade word-of-mouth-forskningen. Föreliggande studie har bidragit till word-of-mouth-forskningen på tre olika sätt: genom 1) bidrag baserat på litteraturanalys, 2) bidrag baserat på empirianalys och 3) bidrag baserat på begreppsligande av informell marknadskommunikation. Min litteraturanalys framställer word-of-mouth-forskningens uppkomst och utveckling i ny dager. Min empirianalys har genererat empiriska begrepp, dels för att beskriva informell marknadskommunikation som företeelse, dels för att beskriva företagens förfarande för att systematisera utnyttjandet av sådan marknadskommunikation. Den begreppsliga kontributionen accentueras i informell marknadskommunikation som ett samlingsbegrepp för olika typer av interkonsumentkommunikation.

Perceived Value of Mobile Service Use and its Consequences

The thesis is positioned in the services marketing field. Previous mobile service research has identified perceived value or relative advantage as a stable predictor of use of services. However, a more detailed view of what customers value in mobile services is needed for marketing diverse types of mobile content and attracting committed customers. The direct relationships between multidimensional value and loyalty constructs have received limited attention in the previous literature, although a multidimensional view is needed for differentiating services. This thesis studies how perceived value of mobile service use affects customer commitment, repurchase intentions, word-of-mouth and willingness to pay. The doctoral thesis consists of three journal articles and one working paper. The four papers have different sub-aims and comprise individual empirical studies. Mixed methods including both personal interviews and survey data collected from end-users of different types of mobile content services are used. The conceptual mobile perceived value model that results from the first explorative empirical study supports a six- dimensional value view. The six dimensions are further categorized into two higher order constructs: content-related perceived value (emotional, social, convenience and monetary value) and context-related (epistemic and conditional value) perceived value. Structural equation modeling is used in the other three studies to validate this framework by analyzing the relationships between context- and content-related value, and how the individual perceived value dimensions affect commitment and behavioral outcomes. Analyzing the direct relationships revealed differences in the effect of perceived value dimensions between information and entertainment mobile service user groups, between effects on commitment, repurchase intentions and word-of-mouth intentions, as well as between effects on commitment to the provider and to the mobile channel as such. This thesis contributes to earlier perceived value literature by structuring the value dimensions into two groups. Most importantly, the thesis contributes to the value and loyalty literature by increasing understanding of how the different dimensions of perceived value directly affect commitment and post-purchase intentions. The results have implications for further theory development in the electronic services field using multidimensional latent constructs, and practical implications for enhancing commitment to content provider and for differentiated marketing strategies in the mobile field. The general conclusion of this thesis is that differentiated value-based marketing of mobile services is essential for attracting committed customers who will use the same providers’ content also in the future. Minna Pihlström is associated with the Centre for Relationship Marketing and Service Management (CERS) at Hanken.

Customer Energy in Relationships

All companies have a portfolio of customer relationships. From a managerial standpoint the value of these customer relationships is a key issue. The aim of the paper is to introduce a conceptual framework for customers’ energy towards a service provider. Customer energy is defined as the cognitive, affective and behavioural effort a customer puts into the purchase of an offering. It is based on two dimensions: life theme involvement and relationship commitment. Data from a survey study of 425 customers of an online gambling site was combined with data about their individual purchases and activity. Analysis showed that involvement and commitment influence both customer behaviour and attitudes. Customer involvement was found to be strongly related to overall spending within a consumption area, whereas relationship commitment is a better predictor of the amount of money spent at a particular company. Dividing the customers into four different involvement / commitment segments revealed differences in churn rates, word-of-mouth, brand attitude, switching propensity and the use of the service for socializing. The framework provides a tool for customer management by revealing differences in fundamental drivers of customer behaviour resulting in completely new customer portfolios. Knowledge of customer energy allows companies to manage their communication and offering development better and provides insight into the risk of losing a customer.

Simulating and Forecasting the Demand for New Consumer Durables

A diffusion/replacement model for new consumer durables designed to be used as a long-term forecasting tool is developed. The model simulates new demand as well as replacement demand over time. The model is called DEMSIM and is built upon a counteractive adoption model specifying the basic forces affecting the adoption behaviour of individual consumers. These forces are the promoting forces and the resisting forces. The promoting forces are further divided into internal and external influences. These influences are operationalized within a multi-segmental diffusion model generating the adoption behaviour of the consumers in each segment as an expected value. This diffusion model is combined with a replacement model built upon the same segmental structure as the diffusion model. This model generates, in turn, the expected replacement behaviour in each segment. To be able to use DEMSIM as a forecasting tool in early stages of a diffusion process estimates of the model parameters are needed as soon as possible after product launch. However, traditional statistical techniques are not very helpful in estimating such parameters in early stages of a diffusion process. To enable early parameter calibration an optimization algorithm is developed by which the main parameters of the diffusion model can be estimated on the basis of very few sales observations. The optimization is carried out in iterative simulation runs. Empirical validations using the optimization algorithm reveal that the diffusion model performs well in early long-term sales forecasts, especially as it comes to the timing of future sales peaks.

Development of Nonsocial Behaviour in the Asiatic Elephant

The elephant calf, a defended follower is completely dependent on adults till the age of 3 months. It begins to explore and attempts to feed at 3 to 6 months, and then becomes partially independent with some feeding on its own. The characteristics of behavior in adults are examined and the development of this pattern in the calf is traced by analyis of duration, transition and clustering of the behavioural elements. Essential activities like suckling, locomotion and lying down for rest appear soon after birth whereas elements of feeding, grooming and play appear only at a later stage. The calf takes the initiative in suckling and its termination, drinking directly by mouth till the age of 6 months. The first element of feeding appears at about a week in attempts to pick up and hold objects in the trunk. Co-ordination of limb, trunk and mouth movement is achieved by about 1 month. The calf is strong enough to pull out plants by 6 months when independent feeding begins. In about a year feeding, drinking and dusting patterns are well developed.

Kädestä suuhun : Makro- ja mikrotaloudellinen tarkastelu suomalaisten kotitalouksien säästämisestä ja sen mittaamisesta 1950-luvulla

This study is divided into two parts: a methodological part and a part which focuses on the saving of households. In the 1950 s both the concepts as well as the household surveys themselves went through a rapid change. The development of national accounts was motivated by the Keynesian theory and the 1940 s and 1950 s were an important time for the development of the national accounts. Before this, saving was understood as cash money or money deposited in bank accounts but the changes in this era led to the establishment of the modern saving concept. Separate from the development of national accounts, household surveys were established. Household surveys have been conducted in Finland from the beginning of the 20th century. At that time surveys were conducted in order to observe the working class living standard and as a result, these were based on the tradition of welfare studies. Also a motivation for undertaking the studies was to estimate weights for the consumer price index. A final reason underpinning the government s interest in observing this data regarded whether there were any reasons for the working class to become radicalised and therefore adopt revolutionary ideas. As the need for the economic analysis increased and the data requirements underlying the political decision making process also expanded, the two traditions and thus, the two data sources started to integrate. In the 1950s the household surveys were compiled distinctly from the national accounts and they were virtually unaffected by economic theory. The 1966 survey was the first study that was clearly motivated by national accounts and saving analysis. This study also covered the whole population rather than it being limited to just part of it. It is essential to note that the integration of these two traditions is still continuing. This recently took a big step forward as the Stiglitz, Sen and Fitoussi Committee Report was introduced and thus, the criticism of the current measure of welfare was taken seriously. The Stiglitz report emphasises that the focus in the measurement of welfare should be on the households and the macro as well as micro perspective should be included in the analysis. In this study the national accounts are applied to the household survey data from the years 1950-51, 1955-56 and 1959-60. The first two studies cover the working population of towns and market towns and the last survey covers the population of rural areas. The analysis is performed at three levels: macro economic level, meso level, i.e. at the level of different types of households, and micro level, i.e. at the level of individual households. As a result it analyses how the different households saved and consumed and how that changed during the 1950 s.

Nonlinear fracture properties of concrete-concrete interfaces

The fracture properties of different concrete-concrete interfaces are determined using the Bazant's size effect model. The size effect on fracture properties are analyzed using the boundary effect model proposed by Wittmann and his co-workers. The interface properties at micro-level are analyzed through depth sensing micro-indentation and scanning electron microscopy. Geometrically similar beam specimens of different sizes having a transverse interface between two different strengths of concrete are tested under three-point bending in a closed loop servo-controlled machine with crack mouth opening displacement control. The fracture properties such as, fracture energy (G(f)), length of process zone (c(f)), brittleness number (beta), critical mode I stress intensity factor (K-ic), critical crack tip opening displacement CTODc (delta(c)), transitional ligament length to free boundary (a(j)), crack growth resistance curve and micro-hardness are determined. It is seen that the above fracture properties decrease as the difference between the compressive strength of concrete on either side of the interface increases. (C) 2010 Elsevier Ltd. All rights reserved.

Kuluttajien kokemukset lastenvaatteiden ja -tarvikkeiden verkkokaupan palvelun laadusta sosiaalisen median keskusteluissa

Tämän pro gradu- tutkielman tavoitteena oli löytää kuluttajien palvelukokemukseen vaikuttavat tekijät lastenvaatteiden- ja tarvikkeiden -verkkokaupassa. Empiirinen tutkimus lähestyi aihetta netnografian avulla. Aineistoksi tähän tutkielmaan valittiin sosiaalisen median keskustelut. Tutkimuksen teoreettinen osa muodostui kolmesta aiheesta: verkko-ostamisesta ja palvelun laadusta, sosiaalisesta mediasta sekä word-of-mouth-viestinnästä. Verkko-ostamisessa käsiteltiin ostamisen eri vaiheet, kuluttajien motivaatiot verkosta ostamiseen, sekä siihen liittyvät riskit ja tarkasteltiin sähköisen palvelun laatua. Sosiaalinen media-luku kertoi sosiaalisen median käytöstä sekä eri medioista. Word-of-mouth-viestintä esitteli perinteisen word-of-mouth-viestinnän lisäksi sähköisen WOM-viestinnän ulottuvuudet. Empiirinen tutkimus oli laadullinen ja se toteutettiin netnografisesti. Netnografia on etnografiaan perustuva menetelmä, jota käytetään internet-aineistoissa. Aineiston analysoinnissa käytettiin teemoittelua. Aihetta lähestyttiin faktanäkökulmasta, eli tutkimuksessa oltiin kiinnostuneita niistä tosiasioista joita keskustelijat kertoivat. Aineisto kerättiin perhe-aiheisten lehtien keskustelupalstoilta sekä blogeista Google-haun avulla. Sosiaalisen median keskustelut valittiin aineistoksi, koska niistä uskottiin saatavan kaikkein totuudenmukaisinta tietoa, johon tutkijan kysymyksen asettelu ei vaikuta. Spontaanit keskustelut antavat erilaista tietoa kuin suoran kysymyksen vastaukset. Tutkimuksen tuloksena löytyi seitsemän teemaa, joita keskusteluissa käsiteltiin. Nämä ovat toimitus, palvelu, palautus ja normalisointi, ulkoasu ja toimivuus, hinta, maksaminen sekä tuotteet ja valikoima. Sen sijaan teorian pohjalta odotettavissa olleet turvallisuus ja yksityisyys eivät tulleet aineistosta lainkaan esiin. Erityisen huonona palveluna asiakkaat pitivät varastosaldojen paikkansapitämättömyyttä, hitaita toimituksia sekä epäystävällistä palvelua. Hyvää palvelua olivat nopeat toimitukset sekä yksilöllinen palvelu ja reklamaatioiden hyvä hoito.

Influence of strain softening on the fracture of plain concrete beams

Fracture behaviour of notched and un-notched plain concrete slender beams subjected to three-point or four-point bending is analyzed through a one-dimensional model, also called Softening Beam Model. Fundamental equations of equilibrium are used to develop the model. The influence of structural size in altering the fracture mode from brittle fracture to plastic collapse is explained through the stress distribution across the uncracked ligament obtained by varying the strain softening modulus. It is found that at the onset of fracture instability, stress at the crack tip is equal to zero. The maximum load and fracture load are found to be different and a unique value for the fracture load is obtained. It is shown that the length of the fracture process zone depends on the value of the strain softening modulus. Theoretical limits for fracture process zone length are also calculated. Several nonlinear fracture parameters, such as, crack tip opening displacement, crack mouth opening displacement and fracture energy are computed for a wide variety of beam specimens reported in the literature and are found to compare very well with experimental and theoretical results. It is demonstrated that by following a simple procedure, both pre-peak and post-peak portions of load versus crack mouth opening displacement curve can be obtained quite accurately. Further, a simple procedure to calculate the maximum load is also developed. The predicted values of maximum load are found to agree well with the experimental values. The Softening Beam Model (SBM), proposed in this investigation is very simple and is based on rational considerations. It can completely describe the fracture process from the beginning of formation of the fracture process zone till the onset of fracture instability.A l'aide d'un modèle unidimensionnel dit ldquoSoftening Beam Modelrdquo (SBM), on analyse le comportement à rupture de poutres élancées pleines entaillées ou non, soumises en flexion en trois ou quatre points. Des équations fondamentales d'équilibre sont utilisées pour développer le modèle. On explique l'influence de la taille du composant sur l'altération du mode de rupture en rupture fragile et en effondrement plastique par la distribution par la distribution des contraintes sur le ligament non fissuré lorsque varie le module d'adoucissement. On trouve que la contrainte à l'extrémité de la fissure est nulle est nulle au début de l'instabilité de la rupture. La charge maximum et la charge à la rupture sont trouvées différentes, et on obtient une valeur unique de la charge à la rupture. On montre que la longueur de la zone concernée par le processus de rupture d'pend de la valeur du module d'adoucissement. On calcule également les limites théoriques de longueur de cette zone. Divers paramètres de rupture non linéaire sont calculés pour une large gamme d'éprouvettes en poutres reprises dans la littérature; on trouve qu'il existe une bonne concordance avec les résultats expérimentaux et théoriques. On démontre qu'en suivant une procédure simple on peut obtenir avec une bonne précision la courbe reliant les portions avant et après le pic de sollicitation en fonction du COD de la fissure. En outre, on développe une procédure simple pour calculer la charge maximum. Les valeurs prédites sont en bon accord avec les valeurs expérimentales. Le modèle SBM proposé est très simple et est basé sur des considérations rationnelles. Il est susceptible de décrire complètement le processus de rupture depuis le début de la formation de la zone intéressée jusqu'à l'amorçage de la rupture instable.

Impact of physical processes on the chlorophyll distribution in the Bay of Bengal

Satellite-derived chlorophyll a concentration (chl a) maps show three regions with high chl a in the Bay of Bengal. First among these is close to the coast, particularly off river mouths, with high values coinciding with the season of peak discharge; second is in the southwestern bay during the northeast monsoon, which is forced by local Ekman pumping; and the third is to the east of Sri Lanka in response to the summer monsoon winds. Chlorophyll-rich water from the mouths of rivers flows either along the coast or in an offshore direction, up to several hundred kilometers, depending on the prevailing ocean current pattern. The Irrawady River plume flows toward offshore and then turns northwestward during October–December, but it flows along the coast into the Andaman Sea for the rest of the year. From the Ganga-Brahmaputra river mouth, chl a–rich water flows directly southward into the open bay during spring but along the Indian coast during summer and winter. Along the Indian coast, the flow of chl a–rich water is determined by the East India Coastal Current (EICC). Whenever the EICC meanders off the Indian coast, it leads to an offshore outbreak of chl a–rich water from the coastal region into open ocean. The EICC as well as open ocean circulation in the bay is made up of several eddies, and these eddies show relatively higher chl a. Eddies near the coast, however, can often have higher chl a because of advection from the coastal region rather than generation within the eddy itself. The bay experiences several cyclones in a year, most of them occurring during October–November. These cyclones cause a drop in the sea surface temperature, a dip in the sea level, and a local increase in chl a. The impact of a cyclone is weaker in the northern part of the bay because of stronger stratification compared to the southern parts.

Structure and conformation of the calcium complex of cyclo(Ala-Leu-Pro-Gly)2 in two crystal forms

Crystal structures of two different forms of the calcium perchlorate complex of cyclo(Ala-Leu-Pro-Gly)2 have been determined and refined using X-ray crystallographic techniques. Orthorhombic form: C32H52N8O8.Ca(ClO4)2.7H2O.2CH3OH, space group C222(1), a = 14.366, b = 18.653, c = 19.824 A, Z = 4, R = 0.068 for 2208 observed reflections. Monoclinic form: C32H52N8O8.Ca(ClO4)2.4H2O, space group C2, a = 21.096, b = 10.182, c = 11.256 A, beta = 103.33 degrees, Z = 2, R = 0.075 for 2165 observed reflections. The cyclic peptide molecule in both the structures has the form of a twofold symmetric, slightly elongated bowl. Type II' beta-turns, involving Gly and Ala at the corners, exist at the two ends of the molecule. The interior of the molecule is substantially hydrophilic, and the external surface of the bowl is largely hydrophobic. The calcium ion is located at the centre of the mouth of the bowl-like molecule. In both crystal forms, four peptide carbonyl oxygens from the cyclic peptide and two solvent oxygens coordinate to the metal ion. The mode of complexation may be described as incomplete encapsulation as, for example, in the case of metal complexes of antamanide. In the crystal structures the complex ions are held together by hydrogen bonds involving perchlorate ions and water molecules. The molecular structure observed in the crystals is entirely consistent with the results of solution studies, which also indicate the conformation of the cyclic peptide in the complex to be similar to that of the uncomplexed molecule.