Pharmacokinetics, efficacy, and safety of pravastatin in children : Studies in children with heterozygous familial hypercholesterolemia and in pediatric cardiac transplant recipients

Background. Hyperlipidemia is a common concern in patients with heterozygous familial hypercholesterolemia (HeFH) and in cardiac transplant recipients. In both groups, an elevated serum LDL cholesterol level accelerates the development of atherosclerotic vascular disease and increases the rates of cardiovascular morbidity and mortality. The purpose of this study is to assess the pharmacokinetics, efficacy, and safety of cholesterol-lowering pravastatin in children with HeFH and in pediatric cardiac transplant recipients receiving immunosuppressive medication. Patients and Methods. The pharmacokinetics of pravastatin was studied in 20 HeFH children and in 19 pediatric cardiac transplant recipients receiving triple immunosuppression. The patients ingested a single 10-mg dose of pravastatin, and plasma pravastatin concentrations were measured up to 10/24 hours. The efficacy and safety of pravastatin (maximum dose 10 to 60 mg/day and 10 mg/day) up to one to two years were studied in 30 patients with HeFH and in 19 cardiac transplant recipients, respectively. In a subgroup of 16 HeFH children, serum non-cholesterol sterol ratios (102 x mmol/mol of cholesterol), surrogate estimates of cholesterol absorption (cholestanol, campesterol, sitosterol), and synthesis (desmosterol and lathosterol) were studied at study baseline (on plant stanol esters) and during combination with pravastatin and plant stanol esters. In the transplant recipients, the lipoprotein levels and their mass compositions were analyzed before and after one year of pravastatin use, and then compared to values measured from 21 healthy pediatric controls. The transplant recipients were grouped into patients with transplant coronary artery disease (TxCAD) and patients without TxCAD, based on annual angiography evaluations before pravastatin. Results. In the cardiac transplant recipients, the mean area under the plasma concentration-time curve of pravastatin [AUC(0-10)], 264.1 * 192.4 ng.h/mL, was nearly ten-fold higher than in the HeFH children (26.6 * 17.0 ng.h/mL). By 2, 4, 6, 12 and 24 months of treatment, the LDL cholesterol levels in the HeFH children had respectively decreased by 25%, 26%, 29%, 33%, and 32%. In the HeFH group, pravastatin treatment increased the markers of cholesterol absorption and decreased those of synthesis. High ratios of cholestanol to cholesterol were associated with the poor cholesterol-lowering efficacy of pravastatin. In cardiac transplant recipients, pravastatin 10 mg/day lowered the LDL cholesterol by approximately 19%. Compared with the patients without TxCAD, patients with TxCAD had significantly lower HDL cholesterol concentrations and higher apoB-100/apoA-I ratios at baseline (1.0 ± 0.3 mmol/L vs. 1.4 ± 0.3 mmol/L, P = 0.031; and 0.7 ± 0.2 vs. 0.5 ± 0.1, P = 0.034) and after one year of pravastatin use (1.0 ± 0.3 mmol/L vs. 1.4 ± 0.3 mmol/L, P = 0.013; and 0.6 ± 0.2 vs. 0.4 ± 0.1, P = 0.005). Compared with healthy controls, the transplant recipients exhibited elevated serum triglycerides at baseline (median 1.3 [range 0.6-3.2] mmol/L vs. 0.7 [0.3-2.4] mmol/L, P=0.0002), which negatively correlated with their HDL cholesterol concentration (r = -0.523, P = 0.022). Recipients also exhibited higher apoB-100/apoA1 ratios (0.6 ± 0.2 vs. 0.4 ± 0.1, P = 0.005). In addition, elevated triglyceride levels were still observed after one year of pravastatin use (1.3 [0.5-3.5] mmol/L vs. 0.7 [0.3-2.4] mmol/L, P = 0.0004). Clinically significant elevations in alanine aminotransferase, creatine kinase, or creatinine ocurred in neither group. Conclusions. Immunosuppressive medication considerably increased the plasma pravastatin concentrations. In both patient groups, pravastatin treatment was moderately effective, safe, and well tolerated. In the HeFH group, high baseline cholesterol absorption seemed to predispose patients to insufficient cholesterol-lowering efficacy of pravastatin. In the cardiac transplant recipients, low HDL cholesterol and a high apoB-100/apoA-I ratio were associated with development of TxCAD. Even though pravastatin in the transplant recipients effectively lowered serum total and LDL cholesterol concentrations, it failed to normalize their elevated triglyceride levels and, in some patients, to prevent the progression of TxCAD.

Nano-confined synthesis of fullerene mesoporous carbon (C60-FMC) with bimodal pores: XRD, TEM, structural properties, NMR, and protein immobilization

Nanoconfined synthesized crystalline fullerene mesoporous carbon (C60-FMC) with bimodal pore architectures of 4.95 nm and 10-15 nm pore sizes characterized by XRD, TEM, nitrogen adsorption/ desorption isotherm and solid-state NMR, and the material was used for protein immobilization. The solid-state 13C NMR spectrum of C60-FMC along with XRD, BET and TEM confirms the formation of fullerene mesoporous carbon structure C60-FMC. The immobilization of albumin (from bovine serum, BSA) protein biomolecule in a buffer solution at pH 4.7 was used to determine the adsorption properties of the C60-FMC material and its structural changes investigated by FT-IR. We demonstrated that the C60-FMC with high surface area and pore volumes have excellent adsorption capacity towards BSA protein molecule. Protein adsorption experiments clearly showed that the C60-FMC with bimodal pore architectures (4.95 nm and 10-15 nm) are suitable material to be used for protein adsorption

Primary polyestradiol phosphate versus orchiectomy for advanced prostate cancer : Studies on the efficacy, cardiovascular complications and prognostic factors

Paikallisesti levinnyttä (T3-4 M0) ja luustoon levinnyttä (T1-4 M1) eturauhassyöpää sairastaneet potilaat satunnaistettiin kirurgiseen kastraatioon (orkiektomia) tai lääkkeelliseen kastraatioon lihaksensisäisellä polyestradiolifosfaatilla (PEP) annoksella 240 mg/kk. Verrattiin hoitojen kliinistä tehoa sekä sydän- ja verisuonikomplikaatioita (SV-komplikaatioita). Verrattiin myös hoitoa edeltäviä plasman testosteroni (T) ja estradioli (E2) pitoisuuksia T3-4 M0 ja T1-4 M1 potilaiden välillä sekä selvitettiin potilaiden yleistilan vaikutusta näihin hormonitasoihin. Lopuksi luotiin T1-4 M1 potilaille eturauhassyövän aiheuttaman kuoleman ennusteellinen riskiluokittelu kolmeen riskiryhmään käyttämällä hoitoa edeltäviä ennustetekijöitä. Kliinisessä tehossa ei orkiektomian ja PEP-hoidon välillä todettu tilastollisesti merkitsevää eroa. Odotetusti T1-4 M1 potilaiden ennuste oli huonompi kuin T3-4 M0 potilaiden. T1-4 M1 potilailla ei ollut SV-kuolemissa hoitoryhmien välillä tilastollista eroa, mutta ei-tappavia SV-komplikaatioita oli PEP ryhmässä (5.9%) enemmän kuin orkiektomia ryhmässä (2.0%). T3-4 M0 potilailla PEP-hoitoon liittyi tilastollisesti merkitsevä SV-kuolleisuus riski orkiektomiaan verrattuna (p = 0.001). PEP ryhmässä 67% kuolemista oli akuutteja sydäninfarkteja. Tämä PEP hoitoon liittyvä sydäninfarktiriski (mukaan lukien myös ei-tappavat sydäninfarktit) oli merkitsevästi pienempi potilailla, joiden hoitoa edeltävä E2 taso oli vähintään 93 pmol/l (p = 0.022). E2 taso oli merkitsevästi matalampi T1-4 M1 potilailla (74.7 pmol/l) kuin T3-4 M0 potilailla (87.9 pmol/l), mutta vastaavaa eroa ei ollut T tasoissa. Sekä T3-4 M0 että T1-4 M1 potilailla yleistilan lasku osittain selitti yksilöllisen T ja E2 tasojen laskun. Eturauhassyövän aiheuttaman kuoleman riskiryhmäluokittelu (Rg) kolmeen ryhmään luotiin käyttämällä alkalista fosfataasia (AFOS), prostata spesifistä antigeenia (PSA), laskoa (La) ja potilaan ikää. Yksi riskipiste annettiin, jos AFOS > 180 U/l (tällä hetkellä käytössä olevalla menetelmällä AFOS > 83 U/l), PSA > 35 µg/l, La > 80 mm/h ja ikä < 60 vuotta. Lopuksi pisteet laskettiin yhteen. Muodostettiin seuraavat ryhmät: Rg-a (0 -1 riskipistettä), Rg-b (2 riskipistettä) ja Rg-c (3 – 4 riskipistettä). Eturauhassyövän aiheuttama kuoleman riski lisääntyi merkitsevästi siirryttäessä riskiryhmästä seuraavaan (p < 0.001). Rg-luokittelu oli kliinisesti käytännöllinen ja hyvä havaitsemaan huonon ennusteen potilaat.

Dielectric properties of some MM′O4 and MTiM′O6 (M=Cr, Fe, Ga; M′=Nb, Ta, Sb) rutile-type oxides

We describe an investigation of the structure and dielectric properties of MM'O-4 and MTiM'O-6 rutile-type oxides for M = Cr, Fe, Ga and M' = Nb. Ta and Sb. All the oxides adopt a disordered rutile structure (P4(2)/mnm) at ambient temperature. A partial ordered trirutile-type structure is confirmed for FeTaO4 from the low temperature (17 K) neutron diffraction studies While both the MM'O-4 oxides (CrTaO4 and FeTaO4) investigated show a normal dielectric property MTiM'O-6 oxides for M = Fe, Cr and M' = Nb/Ta/Sb display a distinct relaxor/relaxor-like response. Significantly the corresponding gallium analogs, GaTiNbO6 and GaTiTaO6, do not show a relaxor response at T<500K (C) 2010 Elsevier Inc All rights reserved

Hyvät pahat pörssiyhtiöt?

Pörssiyhtiöihin liitetään julkisessa keskustelussa usein väitteitä, että pörssiyhtiöt palvelevat osakkeenomistajien lyhytaikaisia etuja muiden sidosryhmien ja myös pitkän aikavälin tuottavuuden kustannuksella. Keskitymme tässä selonteossa tutkimaan onko pörssiyhtiöiden julkisuudessa osalleen saama kritiikki ansaittua. Erityisesti tarkastelemme pörssiyhtiöiden roolia työnantajina ja investoijina 2000- luvulla verrattuna noteeraamattomien yritysten rooliin. Selvitämme myös listattujen ja listaamattomien yritysten eroja sijoituskohteina sekä tutkimme, onko pörssissä ololla vaikutusta yrityksen rahoitusrakenteeseen. Olemme jättäneet vertailun ulkopuolelle nopeasti kasvaneet ja kannattavat tietotekniikka-alan yritykset, joille ei ole olemassa noteeraamattomia vertailukohteita. Lisäksi vertailustamme olemme jättäneet pois yritykset, jotka eivät ole olleet listattuina koko tarkasteluperiodimme aikana. Pois jättämämme kasvuyritykset todennäköisesti parantaisivat pörssiyhtiöiden suhteellista asemaa ainakin kasvu- ja tulosnäkökulmista. Osakkeenomistajien edun lyhytnäköisen valvonnan tulisi johtaa työntekijöiden hyväksikäyttöön ja pitkäaikaisinvestointien karttamiseen. Tuloksemme kuitenkin kertovat päinvastaista. Pörssiyhtiöiden työntekijäkohtaiset henkilökulut ovat selvästi samoilla aloilla toimivia noteeraamattomia yrityksiä korkeammat. Erot ovat huomattavat: pörssiyhtiöiden vuosittaiset henkilökulut ovat noin 3000–4000 euroa suuremmat per henkilö. Lisäksi pörssiyhtiöt ovat kasvattaneet työntekijämääräänsä huomattavasti, toisin kuin noteeraamattomat vertailuyritykset. Otantamme pörssiyhtiöiden kokonaistyöllisyys on 2000-luvulla kasvanut keskimäärin noin 3 % vuodessa. Pörssiyhtiöt työllistivät vuonna 2007 lähes 87.000 työntekijää enemmän kuin vuonna 2001, kun taas yksityisen vertailuryhmän osalta työpaikat olivat samaan aikaan vähentyneet noin 2 500:lla. Pörssiyhtiöiden investoinnit ovat useina vuosina olleet listaamattomia yrityksiä suuremmat, joskin erot kahden ryhmän välillä eivät tyypillisesti ole tilastollisesti merkittäviä. Sidosryhmien hyväksikäytölle tai lyhytjänteisyydelle ei siis tältä osin löydy minkäänlaisia todisteita. Investointituotoissa ei ole järjestelmällisiä eroja kahden ryhmän välillä, lukuunottamatta aivan viime vuosia, jolloin pörssiyhtiöiden oman pääoman tuotto on ollut selvästi korkeampi kuin noteeraamattomien yritysten. Pörssiyhtiöillä ja noteeraamattomilla vertailuyrityksillä on merkittäviä eroja osingonmaksussa. Pörssiyhtiöt maksavat selvästi korkeampia osinkoja kuin vertailuryhmään kuuluvat yritykset. Pörssiyhtiöt maksavat omistajilleen noin puolet nettotuloksistaan osinkoina, kun taas noteeraamattomat yritykset maksavat ainoastaan 20–30 %. Erot pörssiyhtiöiden hyväksi ovat vielä suurempia, kun mittarina käytetään osinkojen suhdetta liikevaihtoon. Tulostemme mukaan pörssiyhtiöt käyttävät velkarahoitusta vastaavia noteeraamattomia yrityksiä enemmän. Tämä voi johtua kahdesta syystä. Ensinnäkin, koska osakkeen julkinen kauppa mahdollistaa omistuspohjan laajenemisen ja alkuperäisyrittäjien sijoitusten paremman hajauttamisen, pörssiyrityksellä on suurempi halukkuus riskinottoon lisäämällä velkarahoitusta. Toisaalta pörssilistaus voi toimia signaalina yrityksen laadusta siten, että rahoittajat tarjoavat velkarahoitusta auliimmin ja paremmilla ehdoilla. Pörssiyhtiöiden suurempi velkaisuus ei ole ollenkaan negatiivinen asia, koska velkarahoitus on verohyötyineen tyypillisesti huomattavasti osakerahoitusta edullisempaa. Tämä taas mahdollistaa lisäinvestointeja, joita ei rahoituksen puutteessa muuten tehtäisi. Yleisemmin rahoitusrakenteiden eroja tarkastellessamme huomaamme viitteitä siitä, että koska pörssiyhtiöillä on mahdollisuus saada osakepääomaa helpommin kuin listaamattomien yhtiöiden, ne pystyvät reagoimaan sekä tuote-, että rahoitusmarkkinoiden 3 mahdollisuuksiin. Listaamattomien yritysten rahoitusrakenne ja myös investoinnit sen sijaan näyttäisivät olevan pitkälle sidonnaisia tulorahoituksen tarjoamiin kassavirtoihin. Pörssiyhtiöt investoivat vähintään yhtä paljon kuin vastaavat noteeraamattomat yritykset ja investointien tuottavuus on vähintään yhtä hyvä. Pörssiyhtiöt ovat parempia palkanmaksajia ja työllistäjiä kuin vastaavat yksityiset yritykset. Pörssiyhtiöt pystyvät maksaamaan selkeästi parempia osinkoja investointien ja muun toiminnan siitä kärsimättä, koska velkarahoituksen parempi saatavuus tai pörssiyhtiöiden suurempi halukkuus käyttää velkarahoitusta tuovat rahoitusrakenteeseen tarvittavaa joustavuutta. Tulostemme valossa arvostelu osakkeenomistajien lyhytaikaisten etujen suosimisesta muiden sidosryhmien tai pitkän aikavälin tuottavuuden kustannuksella ei ole perusteltavissa.

X-ray studies on crystalline complexes involving amino acids and peptides. XV. Crystal structures of L-lysine D-glutamate and L-lysine D-aspartate monohydrate and the effect of chirality on molecular aggregation

L-Lysine D-glutamate crystallizes in the monoclinic space group P2(1) with a = 4.902, b = 30.719, c = 9.679 A, beta = 90 degrees and Z = 4. The crystals of L-lysine D-aspartate monohydrate belong to the orthorhombic space group P2(1)2(1)2(1) with a = 5.458, b = 7.152, c = 36.022 A and Z = 4. The structures were solved by the direct methods and refined to R values of 0.125 and 0.040 respectively for 1412 and 1503 observed reflections. The glutamate complex is highly pseudosymmetric. The lysine molecules in it assume a conformation with the side chain staggered between the alpha-amino and the alpha-carboxylate groups. The interactions of the side chain amino groups of lysine in the two complexes are such that they form infinite sequences containing alternating amino and carboxylate groups. The molecular aggregation in the glutamate complex is very similar to that observed in L-arginine D-aspartate and L-arginine D-glutamate trihydrate, with the formation of double layers consisting of both types of molecules. In contrast to the situation in the other three LD complexes, the unlike molecules in L-lysine D-aspartate monohydrate aggregate into alternating layers as in the case of most LL complexes. The arrangement of molecules in the lysine layer is nearly the same as in L-lysine L-aspartate, with head-to-tail sequences as the central feature. The arrangement of aspartate ions in the layers containing them is, however, somewhat unusual. Thus the comparison between the LL and the LD complexes analyzed so far indicates that the reversal of chirality of one of the components in a complex leads to profound changes in molecular aggregation, but these changes could be of more than one type.

On the relation between rotation increments in different tangent spaces

In computational mechanics, finite rotations are often represented by rotation vectors. Rotation vector increments corresponding to different tangent: spaces are generally related by a linear operator, known as the tangential transformation T. In this note, we derive the higher order terms that are usually left out in linear relation. The exact nonlinear relation is also presented. Errors via the linearized T are numerically estimated. While the concept of T arises out of the nonlinear characteristics of the rotation manifold, it has been derived via tensor analysis in the context of computational mechanics (Cardona and Geradin, 1988). We investigate the operator T from a Lie group perspective, which provides a better insight and a 1-1 correspondence between approaches based on tensor analysis and the standard matrix Lie group theory. (C) 2010 Elsevier Ltd. All rights reserved.

Pyroelectric properties of Bi2VO5.5 ceramic

The dielectric, pyroelectric and thermal properties of ferroelectric Bi2VO5.5(Bi4V2O11) ceramic have been studied over a temperature range of 300-780 K. The sign of the pyroelectric coefficient is positive at room temperature. The dielectric constant, pyroelectric coefficient and specific heat exhibit anomalies around the Curie temperature, 725 K. The frequency response of the dielectric constant and tan delta has been studied over a frequency range of 1-100 kHz. It is found that both the dielectric constant and the loss tangent decrease with increasing frequency. The pyroelectric figures of merit from the point of view of different applications have been calculated at 320 K by combining pyroelectric, dielectric and thermal properties.

Thermodynamic properties of strontium titanates Sr2TiO4, Sr3Ti2O7, Sr4Ti3O10, and SrTiO3

The chemical potentials of SrO in two-phase fields (TiO2 + SrTiO3) (SrTiO3 + Sr4Ti3O10) (Sr4Ti3O10 + Sr3Ti2O7) and (Sr3Ti2O7 + Sr2TiO4) of the pseudo-binary system (SrO + TiO2) have been measured in the temperature range (900 to 1250) K relative to pure SrO as the reference state using solid-state galvanic cells incorporating single crystal SrF2 as the electrolyte The cells were operated under pure oxygen at ambient pressure The standard Gibbs free energies of formation of strontium titanates SrTiO3 Sr4Ti3O10 Sr3Ti2O7 and Sr2TiO4 from their component binary oxides were derived from the reversible electromotive force (EMF) of the cells For the formation of the four compounds from their component oxides TiO2 with rutile structure and SrO the standard Gibbs free energy changes are given by Delta G((ox))(SrTiO3) +/- 89/(J mol(-1)) = -121878 + 3 881(T/K) Delta G((ox))(Sr4Ti3O10) +/- 284/(J mol(-1)) = -409197 + 14 749(T/K) Delta G((ox))(Sr3Ti2O7) +/- 190/(J mol(-1)) = -285827 + 10 022(T/K) Delta G((ox))(Sr2TiO4) +/- 110/(J mol(-1))= -159385 + 3 770(T/K) The reference state for solid TiO2 is the rutile form The results of this study are in good agreement with Gibbs free energy of formation data reported in the literature for SrTiO3 but differ significantly with data for Sr4Ti3O10 For Si3Ti2O7 and Si2TiO4 experimental measurements are not available in the literature for direct comparison with the results obtained in this study (C) 2010 Elsevier Ltd All rights reserved

Growth mechanism of phases by interdiffusion and diffusion of species in the niobium-silicon system

The integrated diffusion coefficient of the phases and the tracer diffusion coefficients of the species are determined in the Nb-Si system by the diffusion couple technique. The diffusion rate of Si is found to be faster than that of Nb in both the NbSi2 and Nb5Si3 phases. The possible atomic mechanism of diffusion is discussed based on the crystal structure and on available details of the defect concentration data. The faster diffusion rate of Si in the Nb5Si3 phase is found to be unusual. The growth mechanism of the phases is also discussed on the basis of the data calculated in this study. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Implications of the recent high statistics determination of the pion electromagnetic form factor in the timelike region

The recently evaluated two-pion contribution to the muon g - 2 and the phase of the pion electromagnetic form factor in the elastic region, known from pi pi scattering by Fermi-Watson theorem, are exploited by analytic techniques for finding correlations between the coefficients of the Taylor expansion at t = 0 and the values of the form factor at several points in the spacelike region. We do not use specific parametrizations, and the results are fully independent of the unknown phase in the inelastic region. Using for instance, from recent determinations, < r(pi)(2)> = (0.435 +/- 0.005) fm(2) and F(-1.6 GeV2) = 0.243(-0.014)(+0.022), we obtain the allowed ranges 3.75 GeV-4 less than or similar to c less than or similar to 3.98 GeV-4 and 9.91 GeV-6 less than or similar to d less than or similar to 10.46 GeV-6 for the curvature and the next Taylor coefficient, with a strong correlation between them. We also predict a large region in the complex plane where the form factor cannot have zeros.

Photolysis of arene chromium tricarbonyl complexes in presence of amine-boranes: Observation of sigma-borane complexes in solution

Activation of the B-H sigma-bond of amine-boranes on the chromium(0) center of arene chromium tricarbonyl complexes (eta(6)-arene) Cr(CO)(3) (arene = fluorobenzene, 1a; benzene, 1b and mesitylene, 1c) has been studied. Photolysis of 1b in presence of ammonia-borane (H3N center dot BH3, AB) and tert-butylamine-borane ((BuH2N)-Bu-t center dot BH3, TBAB) resulted in H-2 evolution and precipitation of a BNHx polymer. On the other hand, photolysis in the presence of trimethylamine-borane (Me3N center dot BH3, TMAB) resulted in the formation of a sigma-borane complex (2) along with Cr(CO)(5)(eta(1)-HBH2 center dot NMe3) (3). The sigma-borane complexes (eta(6)-arene) Cr-( CO)(2)(eta(1)-HBH2 center dot NMe3) (arene = fluorobenzene, 2a; benzene, 2b and mesitylene, 2c) were characterized in solution by H-1, B-11, and C-13 NMR spectroscopy. Electron withdrawing substituents on the arene ring provide the more stable sigma-borane moiety in this series of complexes. (C) 2011 Elsevier B.V. All rights reserved.

Water content - void ratio swell-shrink paths of compacted expansive soils

This paper addresses the behaviour of compacted expansive soils under swell-shrink cycles. Laboratory cyclic swell-shrink tests were conducted on compacted specimens of two expansive soils at surcharge pressures of 6.25, 50.00, and 100.00 kPa. The void ratio and water content of the specimens at several intermediate stages during swelling until the end of swelling and during shrinkage until the end of shrinkage were determined to trace the water content versus void ratio paths with an increasing number of swell-shrink cycles. The test results showed that the swell-shrink path was reversible once the soil reached an equilibrium stage where the vertical deformations during swelling and shrinkage were the same. This usually occurred after about four swell-shrink cycles. The swelling and shrinkage path of each specimen subjected to full swelling - full shrinkage cycles showed an S-shaped curve (two curvilinear portions and a linear portion). However, the swelling and shrinkage path occurred as a part of the S-shaped curve, when the specimen was subjected to full swelling - partial shrinkage cycles. More than 80% of the total volumetric change and more than 50% of the total vertical deformation occurred in the central linear portion of the S-shaped curve. The volumetric change was essentially parallel to the saturation line within a degree of saturation range of 50-80% for the equilibrium cycle. The primary value of the swell-shrink path is to provide information regarding the void ratio change that would occur for a given change in water content for any possible swell-shrink pattern. It is suggested that these swell-shrink paths can be established with a limited number of tests in the laboratory.

Pyrochlore ``dynamic spin-ice'' Pr(2)Sn(2)O(7) and monoclinic Pr(2)Ti(2)O(7): A comparative temperature-dependent Raman study

Here we report a temperature-dependent Raman study of the pyrochlore ``dynamic spin-ice'' compound Pr(2)Sn(2)O(7) and compare the results with its non-pyrochlore (monoclinic) counterpart Pr(2)Ti(2)O(7). In addition to phonon modes, we observe two bands associated with electronic Raman scattering involving crystal field transitions in Pr(2)Sn(2)O(7) at similar to 135 and 460 cm(-1) which couple strongly to phonons. Anomalous temperature dependence of phonon frequencies that are observed in Pyrochlore Pr(2)Sn(2)O(7) are absent in monoclinic Pr(2)Ti(2)O(7). This, therefore, confirms that the strong phonon-phonon anharmonic interactions, responsible for the temperature-dependent anomalous behavior of phonons, arise due to the inherent vacant sites in the pyrochlore structure. (C) 2011 Elsevier Inc. All rights reserved.

Size dependent microstructure for Ag-Ni nanoparticles

The Ag-Ni system is characterized by large differences in atomic sizes (14%) and a positive heat of mixing (+23 kJ mol(-1)). The binary equilibrium diagram for this system therefore exhibits a large miscibility gap in both solid and liquid state. This paper explores the size-dependent changes in microstructure and the suppression of the miscibility gap which occurs when free alloy particles of nanometer size are synthesized by co-reduction of Ag and Ni metal precursors. The paper reports that complete mixing between Ag and Ni atoms could be achieved for smaller nanoparticles (<7 nm). These particles exhibit a single-phase solid solution with face-centered cubic (fcc) structure. With increase in size, the nanoparticles revealed two distinct regions. One of the regions is composed of pure Ag. This region partially surrounds a region of fcc solid solution at an early stage of decomposition. Experimental observations were compared with the results obtained from the thermodynamic calculations, which compared the free energies corresponding to a physical mixture of pure Ag and Ni phases and a fcc Ag-Ni solid solution for different particle sizes. Results from the theoretical calculations revealed that, for the Ag-Ni system, solid solution was energetically preferred over the physical mixture configuration for particle sizes of 7 nm and below. The experimentally observed two-phase microstructure for larger particles was thus primarily due to the growth of Ag-rich regions epitaxially on initially formed small fcc Ag-Ni nanoparticles. (C) 2011 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.