Proton magnetic resonance study of molecular dynamics in (NH4)2CdI4

Proton magnetic resonance and spin-lattice relaxation studies have been carried out on (NH4)2CdI4 as a function of temperature (77–400 K) and Larmor frequency (10, 20 and 30 MHz). The T1 data indicate isotropic tumbling of ammonium ions at equivalent sites till 160 K. There is an indication of a phase transition at 265 K, the activation energy for molecular reorientation increases from 2.8 kcal/mole to 4.6 kcal/mole. The relaxation results and the linewidth data support the presence of two inequivalent sites at low temperatures, one having an environment corresponding to near-rigid-lattice limit and the other undergoing fast reorientations. The behaviour of the free induction decay with temperature below 120 K suggests a coherent motion for the faster species.

A computerized methodology for structural synthesis of kinematic chains: Part 1- Formulation

In an effort to develop a fully computerized approach for structural synthesis of kinematic chains the steps involved in the method of structural synthesis based on transformation of binary chains [38] have been recast in a format suitable for implementation on a digital computer. The methodology thus evolved has been combined with the algebraic procedures for structural analysis [44] to develop a unified computer program for structural synthesis and analysis of simple jointed kinematic chains with a degree of freedom 0. Applications of this program are presented in the succeeding parts of the paper.

Thermally Induced Acyl Migration in Salicylamides. 1. Structures of the Reactants, O-Acetylsalicylamide and O-Benzoylsalicylamide

O-Acetylsalicylamide (Ia), C9H9NO3, M r =179.18, monoclinic, P2Jc, a=8.155(5), b=8.571 (2), c= 13.092 (3)A, fl=99.54 (5) ° , V= 902.4(6)A 3, Z=4, Dm=l.31, Dx=l.319gcm -3, 2(Mo Ka) = 0.71069 A,/~ = 1.08 cm -1, F(000) = 376, T = 295 K, R = 0.076 for 1604 reflections. O-Benzoylsalicylamide (Ib), C14HtlNO 3, M,=241.2, monoclinic, P2t/e, a=9.423(1), b=5.116(1), e= 26.424 (2) A, fl= 103.97 (1)% V= 1236.2 (3)/~3, Z= 4, D~ = 1.28, D x = 1.296 gcm -3, ,;L(Cu Ks) = 1.5418 A, p = 7.71 cm-', F(000) = 504, T= 295 K, R =0.050 for 2115 reflections. The dihedral angles between the amide group and the benzene ring are 39.9 ° (Ia) and 37.9 ° (Ib), whereas between the acyl group and the benzene ring they are 78.1 ° (Ia) and 93.4 ° (Ib). The differences in the packing of the two structures are brought out in terms of the observed hydrogen-bonding patterns. Based on the crystallographic results, an intramolecular mechanism for the migration of the acyl group from the O to the N position is suggested in both compounds.

Minä kirjoittajana : Identiteetit, subjektit ja persoonat lukion 1. vuoden opiskelijoiden omaa kirjoittamista pohdiskelevissa teksteissä

Tutkimuksessani tarkastelen kirjoittajaidentiteettejä teksteissä, joissa lukion ensimmäisen vuoden opiskelijat pohdiskelevat omaa kirjoittamistaan. Lähtökohtanani on ajatus narratiivisesta identiteetistä: identiteetti nähdään hermeneuttisena itsen ymmärtämisen prosessina sen sijaan, että sitä pidettäisiin kuvauksena, jonka totuusarvoa olisi relevanttia arvioida. Tutkimuskohteena on kirjoittajaidentiteetti, joten lähestyn aineistoni tekstejä osana prosessia, jossa ihminen ottaa etäisyyttä omaan kirjoittamiseensa ja siten lisää omaa ymmärrystään siitä. Myös sosiaalinen konteksti vaikuttaa tähän identiteettiprosessiin. Lähestyn kirjoittajaidentiteettejä yhteisöllisestä ja yksilöllisestä näkökulmasta, mutta jaossa ei ole kysymys dikotomiasta vaan kahdenlaisesta valotuksesta samaan asiaan: myös yksilö tarvitsee yhteisön, josta erottua. Yhteisöllisyyttä pohtiessani käsittelen nollapersoonakonstruktiota näkökulman jakamisen ja samastumisen tarjoamisen välineenä. Aineistossani nollapersoonakonstruktio on yhtäältä keino käsitellä omaa kokemusta ja toisaalta keino kurkottaa lukijan puoleen ja saada tämä ymmärtämään kirjoittajaa. Hyvin samanlainen merkitys on aineistossani yleistävällä yksikön 2. persoonalla. Molemmat kielen keinot ilmentävät kirjoittajaidentiteettien sosiaalisuutta: lukija edustaa kirjoittajalle sosiaalista yhteisöä, joka halutaan saada ymmärtämään kirjoittajan ratkaisuja ja kokemuksia. Yhteisöllisyyden valossa tarkastelen myös erilaisia keinoja luoda kirjoittajien kollektiivia. Aineistoni lukiolaiset määrittävät teksteissään erilaisia ryhmiä käyttämällä monikon 1. persoonaa tai passiivia. Monikon 1. persoonaa käyttämällä voidaan luoda myös yhteyttä kirjoittajan ja lukijan välillä. Kirjoittajaidentiteetit näyttäytyvät sosiaalisena, sillä kuuluminen johonkin ryhmään esitetään oman kirjoittamisen kannalta olennaisena asiana. Yksilöllisyyttä tuodaan esiin mm. yksikön 1. persoonaa käyttämällä, kun kirjoittaja asettaa itsensä lausuman subjektiksi, joka erottuu puhuteltavasta sinästä. Kirjoittaja ikään kuin määrittää rajansa ja eronsa suhteessa toiseen. Yksikön 1. persoonan lisäksi myös sana itse nostaa esiin eron muihin. Tässäkin suhteessa kirjoittajaidentiteetit näyttäytyvät sosiaalisina. Erilaisten kielellisten keinojen käyttö tuo näkyviin, kuinka ihminen jäsentää omaa suhdettaan toisiin: mihin hän kuuluu ja mistä hän eroaa. Sosiokulttuurisessa kontekstissa on subjektipositioita, joiden välityksellä identiteetit rakentuvat. Tutkimuksessani pohdin yhteisöllisyyttä ja yksilöllisyyttä myös kahden aineistosta konstruoimani subjektiposition avulla. Ensinnäkin esittelen hyvän kirjoittajan malliposition, johon asettuvan kirjoittajan tekstit ovat mm. pitkiä, monipuolisia ja normatiivisen kieliopin mukaisia. Kirjoittajat suhteuttavat itseään tähän positioon: he joko hyväksyvät sen tai asettuvat vastustamaan sitä. Toiseksi esittelen romanttisen kirjoittajan malliposition, johon liittyy mm. inspiraatio ja kirjoittamisen näkeminen itseilmaisuna. Kirjoittajat projisoivat teksteissään itseään ja omaa kirjoittamistaan suhteessa näihin subjektipositioihin, ja kirjoittajaidentiteetti muodostuu kirjoittajan ja tekstiyhteisön välisessä vuorovaikutuksessa. Avainsanat: kirjoittaminen, identiteetti, nollapersoona, persoonareferenssi

On Coloration of Polyacrylonitrile: A Nuclear Magnetic Resonance Study

Coloration in polyacrylonitrile can be induced in three distinct ways: by heat treatment, by treatment with base, or during synthesis of the polymer itself using ionic initiators at relatively higher temperatures. The present investigation employing 'H and NMR spectroscopy has revealed some common features in colored polyacrylonitrile irrespective of ita mode of coloration. All colored polyacrylonitriles give an additional peak around S 2.7 in 'H NMR spectra and, except for heat-treated polyacrylonitrile, one extra group of peaks in the region 8 12-16 in 13C NMR spectra. The former peak has been attributed to methine and/or methylene protons in branched and/or cyclized structures, while the latter peak has been attributed to methylene carbon atoms in the branched structure. Colorless polyacrylonitriles have been found to be predominantly heterotactic, while colored polyacrylonitriles have been found to have appreciable isotactic contribution.

Diet-induced hypercholesterolemia promotes androgen-independent prostate cancer metastasis via IQGAP1 and caveolin-1

Obesity and metabolic syndrome are associated with several cancers, however, the molecular mechanisms remain to be fully elucidated. Recent studies suggest that hypercholesterolemia increases intratumoral androgen signaling in prostate cancer, but it is unclear whether androgenindependent mechanisms also exist. Since hypercholesterolemia is associated with advanced, castrate-resistant prostate cancer, in this study, we aimed to determine whether and how hypercholesterolemia affects prostate cancer progression in the absence of androgen signaling. We demonstrate that diet-induced hypercholesterolemia promotes orthotopic xenograft PC-3 cell metastasis, concomitant with elevated expression of caveolin-1 and IQGAP1 in xenograft tumor tissues. In vitro cholesterol treatment of PC-3 cells stimulated migration and increased IQGAP1 and caveolin-1 protein level and localization to a detergent-resistant fraction. Down-regulation of caveolin-1 or IQGAP1 in PC-3 cells reduced migration and invasion in vitro, and hypercholesterolemia-induced metastasis in vivo. Double knock-down of caveolin-1 and IQGAP1 showed no additive effect, suggesting that caveolin-1 and IQGAP1 act via the same pathway. Taken together, our data show that hypercholesterolemia promotes prostate cancer metastasis independent of the androgen pathway, in part by increasing IQGAP1 and caveolin-1. These results have broader implications for managing metastasis of cancers in general as IQGAP1 and hypercholesterolemia are implicated in the progression of several cancers.

Genetic characterisation of bovine herpesvirus 1 in New Zealand

AIM: To genotype bovine herpesvirus type 1 (BHV-1) isolates from cattle in New Zealand. METHODS: Twenty-eight BHV-1 isolates were collected from clinical samples from cattle over 28 years. They were characterised and compared using restriction endonuclease analysis (REA), and polymerase chain reaction (PCR) and DNA sequencing. RESULTS: Twenty-four isolates were classified as bovine herpesvirus subtype 1.2b (BHV-1.2b) by REA. The remaining four isolates were distinct from the others in REA profiles of one of the major enzymes (HindIII) by which the classification was made. However, these four isolates were closely related to others when the REA profiles of other restriction enzymes were studied, and therefore were regarded as divergent strains of BHV-1.2b. All BHV-1 isolates were detectable by PCR, and sequence analysis of selected PCR products did not indicate any significant differences between isolates. CONCLUSION: BHV-1.2b appears to be the predominant strain of BHV-1 in cattle in New Zealand. There was no evidence that more virulent strains of BHV-1, e.g. subtype 1.1 and BHV type 5, are, or have been, present in New Zealand. Genetic variations exist among these BHV-1.2b isolates.

High resolution genetic and physical mapping of the I-3 region of tomato chromosome 7 reveals almost continuous microsynteny with grape chromosome 12 but interspersed microsynteny with duplications on Arabidopsis chromosomes 1, 2 and 3

The tomato I-3 gene introgressed from the Lycopersicon pennellii accession LA716 confers resistance to race 3 of the fusarium wilt pathogen Fusarium oxysporum f. sp. lycopersici. We have improved the high-resolution map of the I-3 region of tomato chromosome 7 with the development and mapping of 31 new PCR-based markers. Recombinants recovered from L. esculentum cv. M82 × IL7-2 F2 and (IL7-2 × IL7-4) × M82 TC1F2 mapping populations, together with recombinants recovered from a previous M82 × IL7-3 F2 mapping population, were used to position these markers. A significantly higher recombination frequency was observed in the (IL7-2 × IL7-4) × M82 TC1F2 mapping population based on a reconstituted L. pennellii chromosome 7 compared to the other two mapping populations based on smaller segments of L. pennellii chromosome 7. A BAC contig consisting of L. esculentum cv. Heinz 1706 BACs covering the I-3 region has also been established. The new high-resolution map places the I-3 gene within a 0.38 cM interval between the molecular markers RGA332 and bP23/gPT with an estimated physical size of 50-60 kb. The I-3 region was found to display almost continuous microsynteny with grape chromosome 12 but interspersed microsynteny with Arabidopsis thaliana chromosomes 1, 2 and 3. An S-receptor-like kinase gene family present in the I-3 region of tomato chromosome 7 was found to be present in the microsyntenous region of grape chromosome 12 but was absent altogether from the A. thaliana genome.

The essential and non-essential genes of Bovine herpesvirus 1

Bovine herpesvirus 1 (BoHV-1) is an economically important pathogen of cattle associated with respiratory and reproductive disease. To further develop BoHV-1 as a vaccine vector, a study was conducted to identify the essential and non-essential genes required for in vitro viability. Randominsertion mutagenesis utilizing a Tn5 transposition system and targeted gene deletion were employed to construct gene disruption and gene deletion libraries, respectively, of an infectious clone of BoHV-1. Transposon insertion position and confirmation of gene deletion were determined by direct sequencing. The essential or non-essential requirement of either transposed or deleted open reading frames (ORFs) was assessed by transfection of respective BoHV-1 DNA into host cells. Of the 73 recognized ORFs encoded by the BoHV-1 genome, 33 were determined to be essential and 36 to be non-essential for virus viability in cell culture; determining the requirement of the two dual copy ORFs was inconclusive. The majority of ORFs were shown to conform to the in vitro requirements of BoHV-1 homologues encoded by human herpesvirus 1 (HHV-1). However, ORFs encoding glycoprotein K (UL53), regulatory, membrane, tegument and capsid proteins (UL54, UL49.5, UL49, UL35, UL20, UL16 and UL7) were shown to differ in requirement when compared to HHV-1-encoded homologues.

Texture strengthening in warm-rolled cadmium-1% silver alloy

The variation in the tensile properties at 77 K and 300 K in warm-rolled (300 K) Cd-1% Ag alloy with deformation has been studied in longitudinal as well as transverse specimens. The low-temperature yield strength increases with warm rolling without much loss in ductility. The strength at 300 K, however, decreases with heavy warm deformation. From microstructural studies and X-ray investigations, it was observed that changes in grain size and texture occur during warm rolling. Both these changes are found to be important in deciding the tensile properties. The longitudinal and transverse strengths at 77 K vary linearly with l-frac12, where l is the average grain diameter, and thus they obey the Hall-Petch relation. The Hall-Petch slope, k, is lower in specimens with favourable lcub1013rcub texture while the intercept σo is higher when the lcub0002rcub texture is less favourable.

Evolution of three-dimensional character across the Lan+1NinO3n+1 homologous series with increase in n1

Electrical and magnetic properties of La3Ni2O7 and La4Ni3O10 have been investigated in comparison with those of La2NiO4, LaNiO3, and LaSrNiO4. The results suggest an increasing 3-dimensional character across the homologous series Lan+1NinO3n+1 with increase in n. Accordingly, the electrical resistivity decreases in the order La3Ni2O7, La4Ni3O10, and LaNiO3 and this trend is suggested to be related to the percolation threshold. Magnetic properties of these oxides also show some interesting trends across the series.

Non-linear resonance in strings under narrow band random excitation, part I: Planar response and stability

Non-linear planar response of a string to planar narrow band random excitation is investigated in this paper. A response equation for the mean square deflection σ2 is obtained under a single mode approximation by using the equivalent linearization technique. It is shown that the response is triple valued, as in the case of harmonic excitation, if the centre frequency of excitation Ω lies in a certain specified range. The triple valued response occurs only if the excitation bandwidth β is smaller than a critical value βcrit which is a monotonically increasing function of the intensity of excitation. An approximate method of investigating the almost sure asymptotic stability of the solution is presented and regions of instability in the Ω-σ2 plane have been charted. It is shown that planar response can become unstable either due to an unbounded growth of the in-plane component of motion or due to a spontaneous appearance of an out-of-plane component.

A cryptographic analysis of the TLS 1.3 handshake protocol candidates

The Internet Engineering Task Force (IETF) is currently developing the next version of the Transport Layer Security (TLS) protocol, version 1.3. The transparency of this standardization process allows comprehensive cryptographic analysis of the protocols prior to adoption, whereas previous TLS versions have been scrutinized in the cryptographic literature only after standardization. This is even more important as there are two related, yet slightly different, candidates in discussion for TLS 1.3, called draft-ietf-tls-tls13-05 and draft-ietf-tls-tls13-dh-based. We give a cryptographic analysis of the primary ephemeral Diffie–Hellman-based handshake protocol, which authenticates parties and establishes encryption keys, of both TLS 1.3 candidates. We show that both candidate handshakes achieve the main goal of providing secure authenticated key exchange according to an augmented multi-stage version of the Bellare–Rogaway model. Such a multi-stage approach is convenient for analyzing the design of the candidates, as they establish multiple session keys during the exchange. An important step in our analysis is to consider compositional security guarantees. We show that, since our multi-stage key exchange security notion is composable with arbitrary symmetric-key protocols, the use of session keys in the record layer protocol is safe. Moreover, since we can view the abbreviated TLS resumption procedure also as a symmetric-key protocol, our compositional analysis allows us to directly conclude security of the combined handshake with session resumption. We include a discussion on several design characteristics of the TLS 1.3 drafts based on the observations in our analysis.

Odour sampling 1: Physical chemistry considerations

The selection of an odour sampling device may influence the composition of the resulting odour sample. Limited comparison of emission rates derived from turbulent and essentially quiescent sampling devices confirms that the emission rates derived from these devices are quite different. There is therefore compelling evidence that current odour sampling practice should have greater regard for fundamental physical and chemical principles, the nature of the odour source and the conditions created by the sampling device. Such consideration may identify the most appropriate situations under which the use of these devices may or may not be correct.