The Amenability Studies on Beneficiation of Low Grade Phyllite Deposits of Tungsten From Degana, Rajasthan

The phyllite deposit of Degana, Rajasthan, containing tungsten values in the form of wolframite, (Fe, MnWO sub 4 ) finely dispersed in the quartz groundmass, has been quantitatively analysed to give 0.063% WO sub 3 , 6.66% Fe sub 2 O sub 3 , 14.30% Al sub 2 O sub 3 and 67.4% SiO sub 2 . The major gangue minerals identified are quartz, iron oxides and mica along with minor amounts of graphite, fluorite and sulphides. The amenability of the ore to gravity concentration, magnetic separation and a combination of the processes has been studied. A combination of tabling on --100 mesh ground ore and dry magnetic separation of the tabled concentrate gave a final concentrate containing 1.834% WO sub 3 with an overall recovery of only 4.6%. The complex mineralogy combined with fine dispersion of very low W values have contributed to the low recoveries and grades. Graph, photomicrographs. 10 ref.--AA

Contribution of sea-salt to aerosol optical depth over the Arabian Sea derived from MODIS observations

Making use of aerosol optical depths (AOD) derived from MODIS (onboard TERRA satellite) and winds from NCEP, and the fact that sea-salt optical depth over ocean is determined primarily by sea-surface wind speed, we examine the contribution of sea-salt to the composite aerosol optical depth ( AOD) over Arabian Sea ( AS), by developing empirical models for characterizing wind-speed dependence of sea-salt optical depth. We show that at high wind speeds, sea-salt contributes 81% to the coarse mode and 42% to the composite AOD in the southern AS. In contrast to this, over the northern AS, share of sea-salt to coarse mode and composite optical depth is only 35% and 16% respectively. Comparison of the sea-salt optical depth and coarse mode optical depth ( MODIS) showed excellent agreement. The sea-salt optical depth over AS at moderate to high wind speed is comparable to the anthropogenic AOD reported for this region during winter.

Spectroscopic, microscopic and first rheological investigations in charge-transfer interaction induced organogels

This article describes two-component charge-transfer interaction mediated organogels (CT-gels) derived from anthracene carboxamides obtained from 2-amino 2-hydroxymethyl-1,3-propanediol (TRIS), and 2,3-dialkoxyanthracenes as donors, with 2,4,7-trinitrofluorenone (TNF) as the common acceptor. We demonstrate the versatility of TNF as an electron acceptor in the formation of these gels. The effect of subtle changes in the donor structure on the gelation ability has been investigated by varying the alkyl chain length in the dialkoxyanthracene donors, and by varying the position of the TRIS substituent in the anthracene carboxamide donors. Distinct differences have been observed in the nature of the CT-gels based on these two kinds of anthracene donors. It has been reported in the literature that 2,3-dialkoxyanthracenes form gels on their own in various aliphatic hydrocarbons and alcohols for linear alkyl chains bearing at least 6mcarbon atoms (C-6). In the present study, it is shown that themCT-complex of these molecules with TNF is able to gel many alcoholic and a few hydrocarbon solvents. Also, in the presence of TNF, the 2,3-dialkoxyanthracenes (C-4-C-5) which were non-gelators on their own at ambient temperatures, form CT-gels in a number of alcohols. The other series of gelators discussed, the anthracene carboxamides, require the mandatory presence of TNF to form gels. This donor-acceptor complex forms gels in various aliphatic alcohols. Interestingly, the formation of these CT-gels requires rapid cooling in most of the cases. Thermal stability studies with both types of CT-gels indicate an optimum stoichiometry of 1 : 1 between the donor and the acceptor. Dynamic rheological experiments reveal these gels as viscoelastic soft materials, with the mechanical strength of these gels depending on the amount of TNF present. This provides a means to tune the strength of the gel by varying the doping concentration of the acceptor.

A series of transition metal-azido extended complexes with various anionic and neutral co-ligands: synthesis, structure and their distinct magnetic behavior

The crystal structures and magnetic properties of five new transition metal-azido complexes with two anionic [pyrazine-2-carboxylate (pyzc) and p-aminobenzoate (paba)] and two neutral [pyrazine (pyz) and pyridine (py)] coligands are reported All five complexes were synthesized bysolvothermal methods The complex [Co-2(pyzc)(2)(N-3)(2)(H2O)(2)](n) (1) is 1D and exhibit canted antiferromagnetism, while the 3D complex [MnNa(pyzc)(N-3)(2)(H2O)(2)](n) (2) has a complicated structure and is weakly ferromagnetic in nature [Mn-2(paba)(2)(N-3)(2)(H2O)(2)](n) (3). is a 2D sheet and the Mn-II ions are found to be antiferromagnetically coupled The isostructural 2D complexes [Cu-3(pyz)(2)(N-3)(6)](n) (4) and [Cu-3(py)(2)(N-3)(6)](n) (5) resemble remarkably in their magnetic properties exhibiting moderately strong ferromagnetism. Density functional theory calculations (B3LYP functional) have been performed to provide a qualitative theoretical interpietation of the overall magnetic behavior shown by these complexes.

Interaction of metal ions with 6-oxopurine nucleotides. Part 2. X-Ray structures of ternary nickel(II) complexes with 2'-deoxyguanosine 5'-monophosphate or guanosine 5'-monophosphate

The ternary metal nucleotide complexes [Ni(en)1.3(H2O)1.4(H2O)2][Ni(5?-dGMP)2(en)0.7-(H2O)0.6(H2O)2]·7H2O (1) and [Ni(en)2(H2O)2][Ni(5?-GMP)2(H2O)4]·6H2O (2)(en = ethylenediamine, 5?-dGMP = 2?-deoxyguanosine 5?-monophosphate, 5?-GMP = guanosine 5?-monophosphate) have been prepared and their structures analyzed by X-ray diffraction methods. Both compounds crystallise in the space group C2221 with a= 8.810(1), b= 25.090(4), c= 21.084(1)Å, and Z= 4 for (1) and a= 8.730(1), b= 25.691(4), c= 21.313(5)Å, and Z= 4 for (2). The structures were deduced from the analogous CoIII complexes and refined by full-matrix least-squares methods to final R values of 0.087 and 0.131 for 1 211 and 954 reflections for (1) and (2) respectively. An interesting feature of the deoxyribonucleotide complex (1) is that en is not totally labilized from the metal centre on nucleotide co-ordination, as observed in corresponding ribonucleotide complexes. Apart from extensive intra- and inter-molecular hydrogen bonding, the structures are stabilized by significant intracomplex base�base and base�sugar interactions. The nucleotides in both complexes have an anti base, C(2?)-endo sugar pucker, and gauche�gauche conformation about the C(4?)�C(5?) bond.

Combustion of ammonium perchlorate-based composite propellants in presence of methylammonium perchlorates

The effect of tri- and tetramethylammonium perchlorates (MAP-3 and MAP-4) on the burning rate of ammonium perchlorate (AP) based propellants has been determined at various pressures. Both additives increase the burning rate; however, MAP-3 has a moderate effect, whereas MAP-4 has a rather large effect. To explain the results, the thermal decomposition and calorimetric values of the propellants having these additives have been examined. Compound MAP-3 affects the thermal decomposition rate considerably, whereas MAP-4 has virtually no effect on the decomposition rate. The contrasting effects of MAP-4 on decomposition and burning rate suggest that the enhancement of burning rate may be due to the catalysis of gas-phase reactions. Further, detailed differences between behaviour of MAP-3, and MAP-4 appear to be attributable to the melting and low-temperature exotherm of MAP-3 and nonmelting and high-temperature exotherm of MAP-4.

From Habits to Social Structures : Pragmatism and Contemporary Social Theory

Pragmatism has sometimes been taken as a catchphrase for epistemological stances in which anything goes. However, other authors argue that the real novelty and contribution of this tradition has to do with its view of action as the context in which all things human take place. Thus, it is action rather than, for example, discourses that should be our starting point in social theory. The introductory section of the book situates pragmatism (especially the ideas of G. H. Mead and John Dewey) within the field and tradition of social theory. This introductory also contextualizes the main core of the book which consists of four chapters. Two of these chapters have been published as articles in scientific journals and one in an edited book. All of them discuss the core problem of social theory: how is action related to social structures (and vice versa)? The argument is that habitual action is the explanation for the emergence of social structures from our action. Action produces structures and social reproduction takes place when action is habitualized; that is, when we develop social dispositions to act in a certain manner in familiar environments. This also means that even though the physical environment is the same for all of us, our habits structure it into different kinds of action possibilities. Each chapter highlights these general insights from different angles. Practice theory has gained momentum in recent years and it has many commonalities with pragmatism because both highlight the situated and corporeal character of human activity. One famous proponent of practice theory is Margaret Archer who has argued that the pragmatism of G. H. Mead leads to an oversocialized conception of selfhood. Mead does indeed present a socialized view of selfhood but this is a meta-sociological argument rather than a substantial sociological claim. Accordingly, one can argue that in this general sense intersubjectivity precedes subjectivity and not the other way around. Such a view does not indicate that our social relation would necessarily "colonize" individual action because there is a place for internal conversations (in Archer s terminology); it is especially in those phases of action where it meets obstacles due to the changes of the environment. The second issue discussed has the background assumption that social structures can fruitfully be conceptualized as institutions. A general classification of different institution theories is presented and it is argued that there is a need for a habitual theory of institutions due to the problems associated with these other theories. So-called habitual institutionalism accounts for institutions in terms of established and prevalent social dispositions that structure our social interactions. The germs of this institution theory can be found in the work of Thorstein Veblen. Since Veblen s times, these ideas have been discussed for example, by the economist Geoffrey M. Hodgson. His ideas on the evolution of institutions are presented but a critical stance is taken towards his tendency of defining institutions with the help of rules because rules are not always present in institutions. Accordingly, habitual action is the most basic but by no means the only aspect of institutional reproduction. The third chapter deals with theme of action and structures in the context of Pierre Bourdieu s thought. Bourdieu s term habitus refers to a system of dispositions which structure social fields. It is argued that habits come close to the concept of habitus in the sense that the latter consists of particular kinds of habits; those that are related to the reproduction of socioeconomic positions. Habits are thus constituents of a general theory of societal reproduction whereas habitus is a systematic combination of socioeconomic habits. The fourth theme relates to issues of social change and development. The capabilities approach has been associated with the name of Amartya Sen, for example, and it underscores problems inhering in economistic ways of evaluating social development. However, Sen s argument has some theoretical problems. For example, his theory cannot adequately confront the problem of relativism. In addition, Sen s discussion lacks also a theory of the role of the public. With the help of arguments derived from pragmatism, one gets an action-based, socially constituted view of freedom in which the role of the public is essential. In general, it is argued that a socially constituted view of agency does not necessarily to lead to pessimistic conclusions about the freedom of action.

Preterm birth and risk factors for chronic disease : Helsinki Study of Very Low Birth Weight Adults

Background: The improved prognosis of early preterm birth has created a generation of surviving very low birth weight (< 1500 g, VLBW) infants whose health risks in adulthood are poorly known. Of every 1000 live-born infants in Finland, about 8 are born at VLBW. Variation in birth weight, even within the normal range, relates to considerable variation in the risk for several common adult disorders, including cardiovascular disease and osteoporosis. Small preterm infants frequently exhibit severe postnatal or prenatal growth retardation, or both. Much reason for concern thus exists, regarding adverse health effects in surviving small preterm infants later lives. We studied young adults, aiming at exploring whether VLBW birth and postnatal events after such a birth are associated with higher levels of risk factors for cardiovascular disease or osteoporosis. Subjects and Methods: A follow-up study for VLBW infants began in 1978; by the end of 1985, 335 VLBW survivors at Helsinki University Central Hospital participated in the follow-up. Their gestational ages ranged from 24 to 35 weeks, mean 29.2 and standard deviation 2.2 weeks. In 2004, we invited for a clinic visit 255 subjects, aged 18 to 27, who still lived in the greater Helsinki area. From the same birth hospitals, we also invited 314 term-born controls of similar age and sex. These two study groups underwent measurements of body size and composition, function of brachial arterial endothelium (flow-mediated dilatation, FMD) and carotid artery intima-media thickness (cIMT) by ultrasound. In addition, we measured plasma lipid concentrations, ambulatory blood pressure, fasting insulin, glucose tolerance and, by dual-energy x-ray densitometry, bone-mineral density. Results: 172 control and 166 VLBW participants underwent lipid measurements and a glucose tolerance test. VLBW adults fasting insulin (adjusted for body mass index) was 12.6% (95% confidence interval, 0.8 to 25.8) higher than that of the controls. The glucose and insulin concentrations 120 minutes after 75 g glucose ingestion showed similar differences (N=332) (I). VLBW adults had 3.9 mmHg (1.3 to 6.4) higher office systolic blood pressure, 3.5 mmHg (1.7 to 5.2) higher office diastolic blood pressure (I), and, when adjusted for body mass index and height, 3.1 mmHg (0.5 to 5.5) higher 24-hour mean systolic blood pressure (N=238) (II). VLBW birth was associated neither with HDL- or total cholesterol nor triglyceride concentrations (N=332) (I), nor was it associated with a low FMD or a high cIMT (N=160) (III). VLBW adults had 0.51-unit (0.28 to 0.75) lower lumbar spine Z scores and 0.56-unit (0.34 to 0.78) lower femoral neck Z scores (N=283). Adjustments for size attenuated the differences, but only partially (IV). Conclusions: These results imply that those born at VLBW, although mostly healthy as young adults, already bear several risk factors for chronic adult disease. The significantly higher fasting insulin level in adults with VLBW suggests increased insulin resistance. The higher blood pressure in young adults born at VLBW may indicate they later are at risk for hypertension, although their unaffected endothelial function may be evidence for some form of protection from cardiovascular disease. Lower bone mineral density around the age of peak bone mass may suggest increased risk for later osteoporotic fractures. Because cardiovascular disease and osteoporosis are frequent, and their prevention is relatively cheap and safe, one should focus on prevention now. When initiated early, preventive measures are likely to have sufficient time to be effective in preventing or postponing the onset of chronic disease.

Preterm birth and risk factors for chronic disease : Helsinki Study of Very Low Birth Weight Adults

Background: The improved prognosis of early preterm birth has created a generation of surviving very low birth weight (PIENEMPI KUIN 1500 g, VLBW) infants whose health risks in adulthood are poorly known. Of every 1000 live-born infants in Finland, about 8 are born at VLBW. Variation in birth weight, even within the normal range, relates to considerable variation in the risk for several common adult disorders, including cardiovascular disease and osteoporosis. Small preterm infants frequently exhibit severe postnatal or prenatal growth retardation, or both. Much reason for concern thus exists, regarding adverse health effects in surviving small preterm infants later lives. We studied young adults, aiming at exploring whether VLBW birth and postnatal events after such a birth are associated with higher levels of risk factors for cardiovascular disease or osteoporosis. Subjects and Methods: A follow-up study for VLBW infants began in 1978; by the end of 1985, 335 VLBW survivors at Helsinki University Central Hospital participated in the follow-up. Their gestational ages ranged from 24 to 35 weeks, mean 29.2 and standard deviation 2.2 weeks. In 2004, we invited for a clinic visit 255 subjects, aged 18 to 27, who still lived in the greater Helsinki area. From the same birth hospitals, we also invited 314 term-born controls of similar age and sex. These two study groups underwent measurements of body size and composition, function of brachial arterial endothelium (flow-mediated dilatation, FMD) and carotid artery intima-media thickness (cIMT) by ultrasound. In addition, we measured plasma lipid concentrations, ambulatory blood pressure, fasting insulin, glucose tolerance and, by dual-energy x-ray densitometry, bone-mineral density. Results: 172 control and 166 VLBW participants underwent lipid measurements and a glucose tolerance test. VLBW adults fasting insulin (adjusted for body mass index) was 12.6% (95% confidence interval, 0.8 to 25.8) higher than that of the controls. The glucose and insulin concentrations 120 minutes after 75 g glucose ingestion showed similar differences (N=332) (I). VLBW adults had 3.9 mmHg (1.3 to 6.4) higher office systolic blood pressure, 3.5 mmHg (1.7 to 5.2) higher office diastolic blood pressure (I), and, when adjusted for body mass index and height, 3.1 mmHg (0.5 to 5.5) higher 24-hour mean systolic blood pressure (N=238) (II). VLBW birth was associated neither with HDL- or total cholesterol nor triglyceride concentrations (N=332) (I), nor was it associated with a low FMD or a high cIMT (N=160) (III). VLBW adults had 0.51-unit (0.28 to 0.75) lower lumbar spine Z scores and 0.56-unit (0.34 to 0.78) lower femoral neck Z scores (N=283). Adjustments for size attenuated the differences, but only partially (IV). Conclusions: These results imply that those born at VLBW, although mostly healthy as young adults, already bear several risk factors for chronic adult disease. The significantly higher fasting insulin level in adults with VLBW suggests increased insulin resistance. The higher blood pressure in young adults born at VLBW may indicate they later are at risk for hypertension, although their unaffected endothelial function may be evidence for some form of protection from cardiovascular disease. Lower bone mineral density around the age of peak bone mass may suggest increased risk for later osteoporotic fractures. Because cardiovascular disease and osteoporosis are frequent, and their prevention is relatively cheap and safe, one should focus on prevention now. When initiated early, preventive measures are likely to have sufficient time to be effective in preventing or postponing the onset of chronic disease.

Synthetic and conformational studies on dehydrophenylalanine containing model peptides

Four model dipeptides containing a Z-dehydrophenylalanine residue (ΔZPhe) at the C-terminal, Boc-X-ΔZ Phe-NHMe (X = Ala (1), Gly (2), Pro (3), and Val (4)), have been synthesised and their solution conformations investigated by 270 MHz 1H n.m.r. and i.r. spectroscopy. N.m.r. studies on these peptides clearly show the presence of intramolecularly hydrogen bonded structures in CHCl3 solutions while such structures appear to be absent in the corresponding saturated peptides. This conclusion is also supported by i.r. studies. Studies of the nuclear Overhauser effect provided evidence for the occurrence of a significant population of β-turn structures in solvents like CDCl3 and (CD3)2SO. The observed NOES are consistent with a major contribution from Type II β-turn structure in CDCl3, while in (CD3)2SO solutions there is evidence of a partially extended structure also.

Electromagnetic wave propagation at the interface between two polar semiconductors

The interface between two polar semiconductors can support three types of phonon-plasmon-polariton modes propagating in three well-defined frequency windows ??1?[min(?1,?3),?R1], ??2?[max(?2,?4),?R2], and ??3?[min(?2,?4),?R3]. The limiting frequencies ?1,2,3,4 are defined by ?1(?)=0, ?2(?)=0, and ?R1,2,3 by ?1(?)+?2(?)=0, where ?i(?) are dielectric functions of the two media with i=1,2. The dispersion, decay distances, and polarization of the three modes are discussed. The variation of the limiting frequencies with the interface plasma parameter ???p22/?p12 reveals an interesting feature in the dispersion characteristics of these modes. For the interfaces for which the bulk coupled phonon-plasmon frequencies of medium 1 are greater than the LO frequency or are less than the TO frequency of medium 2, there exist two values of ?=?1 and ?2(

Iäkkäiden lääkehoitoihin liittyvien riskien kartoittaminen – Arviointityökalun kehittäminen Delfoi-menetelmällä

Tutkimuksen taustalla on väestön ikääntyminen ja iäkkäiden lisääntynyt lääkkeiden käyttö. Ikääntyminen aiheuttaa elimistössä useita muutoksia, jotka voivat muuttaa lääkevastetta ja altistaa potilaan haittavaikutuksille. Iäkkäillä riski joutua sairaalaan lääkkeen haittavaikutuksen vuoksi on arvioitu olevan neljä kertaa suurempi kuin nuoremmilla. Monet lääkkeiden yhteis- ja haittavaikutukset olisivat ehkäistävissä välttämällä iäkkäillä tiettyjä lääkeaineita. Iäkkäiden lääkehoitojen seurantaa ja arviointia varten on kehitetty erilaisia suosituksia sekä Suomessa että kansainvälisesti. Tutkimuksen tavoitteena oli luoda Suomen oloihin soveltuva, hoitajien koulutettuina käytettävissä oleva, avohoidon yli 65-vuotiaiden iäkkäiden lääkitykseen liittyviä riskejä arvioiva työkalu. Työkalun avulla voitaisiin löytää ne potilaat, joiden lääkitykseen liittyy paljon riskejä. Tutkimuksen aineistona olivat laaja kansainvälinen kirjallisuuskatsaus iäkkäiden lääkehoitoihin liittyvistä tekijöistä sekä asiantuntijakommentoinnit, joiden perusteella luotiin alustava arviointityökalu. Alustava arviointityökalu validoitiin kolmikierroksisella Delfoi-menetelmällä. Delfoi-menetelmä on laadullinen konsensusmenetelmä, joka perustuu asiantuntijoiden arvioihin tutkittavasta asiasta. Kaksi ensimmäistä Delfoi-kierrosta mittasivat alustavan arviointityökalun kohtien soveltuvuutta ja kolmas kierros kohtien tärkeyttä arvioitaessa iäkkään lääkityksiin liittyviä riskejä. Tutkimuksen Delfoi-kierroksien vastaajiksi pyydettiin 33 geriatrian asiantuntijaa, joista vastaajiksi lupautui 11 lääkäriä, 3 proviisoria ja 4 sairaanhoitajaa. Delfoi-kierrosten tuloksia analysoitiin sekä kvantitatiivisesti että kvalitatiivisesti. Tutkimuksen tuloksena saatu arviointityökalu käsittää 19 iäkkäiden lääkehoitoa arvioivaa kohtaa. Asiantuntijapaneelin mukaan kaikki arviointityökalun lääkitykseen liittyviä riskejä mittaavat kohdat ovat tärkeitä tai jokseenkin tärkeitä, joten työkalun voidaan olettaa olevan validi mitattaessa lääkitykseen liittyviä riskejä. Jatkotutkimuksissa työkalun käytettävyyttä sekä riskien mittaamiskykyä tulee testata sekä arviointityökalun käyttäjien että potilaiden keskuudessa. Kehitettyä työkalua voidaan jatkossa hyödyntää esimerkiksi koulutustarkoituksissa sen varsinaisen käyttötarkoituksen lisäksi. Työkalun avulla iäkkäiden lääkehoitoa voidaan tulevaisuudessa toteuttaa entistä turvallisemmin ja tarkoituksenmukaisemmin.

Complexation of siRNA with Dendrimer: A Molecular Modeling Approach

This paper reports the structural behavior and thermodynamics of the complexation of siRNA with poly(amidoamine) (PAMAM) dendrimers of generation 3 (G3) and 4 (G4) through fully atomistic molecular dynamics (MD) simulations accompanied by free energy calculations and inherent structure determination. We have also done simulation with one siRNA and two dendrimers (2 x G3 or 2xG4) to get the microscopic picture of various binding modes. Our simulation results reveal the formation of stable siRNA-dendrimer complex over nanosecond time scale. With the increase in dendrimcr generation, the charge ratio increases and hence the binding energy between siRNA and dendrimer also increases in accordance with available experimental measurements. Calculated radial distribution functions of amines groups of various subgenerations in a given generation of dendrimer and phosphate in backbone of siRNA reveals that one dendrimer of generation 4 shows better binding with siRNA almost wrapping the dendrimer when compared to the binding with lower generation dendrimer like G3. In contrast, two dendrimers of generation 4 show binding without siRNA wrapping the den-rimer because of repulsion between two dendrimers. The counterion distribution around the complex and the water molecules in the hydration shell of siRNA give microscopic picture of the binding dynamics. We see a clear correlation between water. counterions motions and the complexation i.e. the water molecules and counterions which condensed around siRNA are moved away from the siRNA backbone when dendrimer start binding to the siRNA back hone. As siRNA wraps/bind to the dendrimer counterions originally condensed onto siRNA (Na-1) and dendrimer (Cl-) get released. We give a quantitative estimate of the entropy of counterions and show that there is gain in entropy due to counterions release during the complexation. Furthermore, the free energy of complexation of IG3 and IG4 at two different salt concentrations shows that increase in salt concentration leads to the weakening of the binding affinity of siRNA and dendrimer.

Conformations of the amino terminal tetrapeptide of emerimicins and antiamoebin in solution and in the solid state

The conformations of Boc-l-Phe-(AiB)3-OH (1) and Boc-l-Phe-(Aib)3-OMe (2) which correspond to the amino terminal sequence of the emerimicins and antiamoebins have been studied in solution using 270 MHz 1H n.m.r. In dimethyl sulphoxide solution both peptides show the presence of two strongly solvent shielded Aib NH groups, consistent with a consecutive β-turn conformation, involving the Aib(3) and Aib(4) NH groups in intramolecular 4 → I hydrogen bonds. This folded conformation is maintained for 2 in chloroform solution. Nuclear Overhauser effect studies provide evidence for a Type II Phe-Aib β-turn. An X-ray diffraction study of Boc-(d,l)-Phe-(Aib)3-OH establishes a single type III(III′) β-turn conformation with Aib(2)-Aib(3) as the corner residues. A single intramolecular 4 → I hydrogen bond between Phe(I) CO and Aib(4) NH groups is observed in the crystal. The solution conformation may incorporate a consecutive type II-III′ structure for the Phe(1)-Aib(2)-Aib(3) segment, with the initial type II β-turn being destabilized by intermolecular interactions in the solid state.

Conformations of dehydrophenylalanyl containing peptides. Nuclear Overhauser effect study of two acyclic

Two isomeric, acyclic tetrapeptides containing a Z-dehydrophenylalanine residue (Δz-Phe) at position 2 or 3, Boc-Leu-Ala-Δz-Phe-Leu-OMe (1) and Boc-Leu-Δz-Phe-Ala-Leu-OMe (2), have been synthesized and their solution conformations investigated by 270MHz 1H n.m.r. spectroscopy. In peptide 1 the Leu(4) NH group appears to be partially shielded from solvent, while in peptide 2 both Ala(3) and Leu(4) NH groups show limited solvent accessibility. Extensive difference nuclear Overhauser effect (n.O.e.) studies establish the occurrence of several diagnostic inter-residue n.O.e.s (CαjH ⇆ Ni+1H and NiH ⇆ Ni+1H) between backbone protons. The simultaneous observation of “mutually exclusive” n.O.e.s suggests the presence of multiple solution conformations for both peptides. In peptide 1 the n.O.e. data are consistent with a dynamic equilibrium between an -Ala-Δz-Phe- Type II β-turn structure and a second species with Δz-Phe adopting a partially extended conformation with Ψ values of ± 100° to ± 150°. In peptide 2 the results are compatible with an equilibrium between a highly folded consecutive β-turn structure for the -Leu-Δz-Phe-Ala- segment and an almost completely extended conformation.