Raman spectrum of triglycine selenate (G3Se), [(NH2CH2COOH)3 H2SeO4]

The Raman spectrum of a single crystal of triglycine selenate G3Se which is ferroelectric below 22° C. has been photographed using λ 2537 excitation. 42 Raman lines have been recorded of which 6 belong to the lattice spectrum, 3 are due to NH...O oscillations and the remaining 33 are due to internal oscillations of the ions of glycine and SeO4--. There is a close similarity between the spectrum of triglycine selenate and the spectrum of its isomorph, triglycine sulphate, the frequency shifts due to the SO4-- ion being replaced by the frequency shifts due to the SeO4-- ion. The existence of glycine in the zwitterion form in the structure of G3Se is substantiated by the appearance in the Raman spectrum of lines which are attributable to NH3+ groups and COO- groups. The appearance of the additional C-H line at 2982 cm.-1 in the spectrum of triglycine selenate which is absent in the spectrum of α-glycine indicates the existence of planar monoprotonated glycine also in the structure, as indicated by X-ray studies.

Hydrolytic reactions of tetrasulphur tetranitride in a homogeneous medium

The hydrolytic reactions of tetrasulphur tetranitride are studied in a homogeneous medium. Alkaline hydrolysis gives sulphite, thiosulphate, sulphate and sulphide whereas the products in acid hydrolysis are mainly sulphur dioxide, elemental sulphur and hydrogen sulphide, with traces of polythionates. Under optimum conditions, tetrasulphur tetranitride reacts with sulphite consuming 2 moles of sulphite per mole of sulphur nitride to give 2 moles of trithionate. The reaction of sulphur nitride with thiosulphuric acid gives pentathionate and tetrathionate.

Mechanism of crystal structure transformations. Part 3. - Factors affecting the anatase-rutile transformation

The particle size and crystallite size of anatase increase markedly in the region of the crystal structure transformation. The unit cell of anatase seems to expand prior to the transformation to rutile. This expansion has been attributed to a displacive transformation of the type defined by Buerger. Smaller particle size and larger surface area seem to favour the transformation. The kinetics of the transformation of anatase prepared by the hydrolysis of titanium sulphate have been studied at different temperatures and are found to be considerably different from the kinetics of the transformation of pure anatase. The transformation becomes immeasurably slow below ∼695 ± 10°C compared to ∼610°C for pure anatase. An induction period is observed in the transformation of anatase obtained from sulphate hydrolysis and the duration decreases with increase in temperature. The activation energy is ∼120 kcal/mole, a value higher than that for the pure anatase-rutile transformation. The results have been interpreted in terms of the relative rates of nucleation and propagation processes. The activation energy for the nucleation process seems to be much larger than for the propagation process. The kinetics of the transformation of anatase samples doped with different amounts of sulphate ion impurity have also been studied and the transformation is found to be progressively decelerated with increase in the impurity concentration. The energy of activation for the transformation appears to increase progressively with increase in impurity concentration.

Raman spectra of crystalline double sulphates Part II. Ammonium double sulphates

Raman spectra of single crystals of (NH4)2M(SO4)2·6 H2O where M=Mg, Zn Ni or Co have been recorded using λ 2537 excitation. Interesting results concerning the substitution of the divalent atoms in the double sulphate lattice on the sulphate and ammonium frequencies are observed. The spectra of these double sulphates are discussed in the light of the known crystal structure details and in relation, to the spectra of the corresponding potassium double sulphates, reported recently by the author. The Raman spectrum of NaNH4SO4·2 H2O has also been recorded for the first time and the results obtained are also included.

Isolation and partial characterization of sheep plasma α1-mucoprotein

1. 1. Sheep plasma α1-mucoprotein was isolated in an electrophoretically homogeneous state by a combination of ammonium sulphate saturation, isoelectric precipitation and preparative agar electrophoresis in a yield of approx. 150 mg/l of plasma. 2. 2. The mucoprotein was water-soluble, non-coagulable on heating at 100°, not precipitable by 1.8 M perchloric acid, 10% trichloroacetic acid but precipitable by saturated ammonium sulphate solution, 0.6 M sulfosalicylic acid and 5% phosphotungstic acid in 2 N HCl. It had E1 cm1 % value of 9.57 at 278 mμ in water, refractive-index index increment 1.9·10-4 (g/l) in water, isoelectric point at pH 4.45 (sodium acetate-acetic acid buffer) and was homogeneous in pH range 4.0-11.5 but at pH values 2.6 and 3.5 showed some dissociation. 3. 3. The mucoprotein had the following chemical composition: Nitrogen, 12.4%; polypeptide, 77.4%; total hexose (only mannose and galactose), 7.1%; fucose, 1.0%; glucosamine, 4.9% and sialic acid, 4.8%. It had no N-terminal amino acid.

Raman spectra of crystalline double sulphates

Raman spectra of single crystals of K2M(SO4)2 · 6 H2O where M=Mg, Zn, Ni or Co have been recorded for the first time using λ 2537 as the exciting radiation. The corresponding five single sulphates have also been studied. Interesting results concerning the substitution of magnesium, zinc, nickel or cobalt in the double sulphate lattice on the sulphate frequencies are observed. The lattice spectra of these double sulphates are analysed group theoretically and discussed in relation to the lattice spectra of the corresponding individual sulphates. Certain new results concerning the Raman spectra of the individual sulphates have also been obtained and in the case of CoSO4 · 7 H2O the spectrum has been recorded for the first time.

Raman spectra of addition compounds of glycine (diglycine hydrochloride, diglycine hydrobromide and diglycine nitrate)

Raman spectra of single crystals of diglycine hydrochloride, diglycine hydrobromide and diglycine nitrate have been recorded for the first time. λ 2536·5 resonance radiation of mercury has been used as exciter. The spectrum of diglycine hydrochloride exhibits 10 low frequency lines and 41 lines due to internal oscillations, while that of diglycine hydrobromide exhibits 11 lines and 41 lines respectively. In the case of diglycine nitrate 46 lines have been recorded, of which 10 belong to the lattice spectrum. These spectra are compared with the Raman spectra of triglycine sulphate and α-glycine and proper assignments have been given to the internal oscillations.

Lihaluujauhon soveltuvuus sokerijuurikkaan lannoitteeksi

Lihaluujauho muodostaa maatilojen myytävien kasvi- ja eläinperäisten tuotteiden jälkeen tärkeimmän agroekosysteemeistä poispäin suuntautuvan ravinnevirran. Se sisältää runsaasti pääkasvinravinteita typpeä, fosforia ja kalsiumia (N ~8%, P ~5%, Ca yleensä ~10-15% luuaineksen määrästä riippuen), sekä kaliumia n.1% tai alle. Lihaluujauho on todettu tehokkaaksi lannoitteeksi useilla viljelykasveilla ja sen käyttö on sallittu myös luomuviljelyssä EU-alueella. Lihaluujauhoon ja erityisesti sen rehukäyttöön liittyvistä riskeistä merkittävin on TSE-tautien riski (naudan BSE-, lampaiden ja vuohien scrapie-, sekä ihmisen vCJD-taudit). Rehukäyttöä on monissa maissa rajoitettu 1980-luvulla puhjenneen BSE-kriisin myötä. BSE-taudin leviäminen yhdistettiin tilanteeseen, jossa nautaperäistä lihaluujauhoa käytettiin nautaeläinten rehun ainesosana. Myös lihaluujauhon käytössä turkiseläinrehuna saattaa piillä BSE:n tai muun TSE-taudin riski. Oikein käsitellyn lihaluujauhon lannoitekäyttöön ei kuitenkaan näytä tarkastelemieni tutkimusten perusteella sisältyvän huomattavaa TSEriskiä, jos huolehditaan asianmukaisista varotoimista ja menettelyistä sekä tuotteen valmistusprosessissa, että käytettäessä lannoitetta. Lihaluujauhon lannoitekäytön lisääminen edistäisi ruokajärjestelmämme ravinnekierron sulkemista etenkin fosforin osalta. Lihaluujauho on uusiutuva luonnonvara, jonka lannoitekäytöllä voitaisiin korvata huomattava osa lannoiteaineena kulutettavista fosforipitoisista kiviaineista. Sokerijuurikkaan lannoituskokeissa Varsinais-Suomen Kaarinassa vuosina 2008 ja 2009 lihaluujauhokäsittelyt eivät menestyneet aivan yhtä hyvin satotasovertailussa kuin kontrollikäsittelyiden NPK-väkilannoitteet, mutta laatuominaisuuksiltaan (sokeripitoisuus, amino-N, K, ja Na-pitoisuudet) joiltakin osin kontrollikäsittelyjä paremmin. Kokeissa käytetyt lajikkeet olivat ’Jesper’ vuonna 2008 ja ’Lincoln’ vuonna 2009. Käytetty lihaluujauholannoite oli Honkajoki Oy:n Viljo Yleislannoite 8-4-3, joka sisälsi noin 10% kaliumsulfaatin ja kasviperäisten sivutuotteiden seosta. Viljo-lannoitetta käytettiin sekä yksistään, että yhdistettynä 10-25%:iin väkilannoitetta. Vuoden 2009 Viljo-koejäseniin vielä lisättiin kaliumsulfaattilannoitetta (42% K, 18% S), jotta päästiin annetun kaliumin määrässä päästiin lannoitussuosituksen (60 kg K/ha) tasolle. Pelkkä Viljo-lannoite tuotti merkitsevästi alhaisemmat sadot kuin kontrollikäsittelyt molempina vuosina. Kuitenkin kun Viljolannoitteen ohella käytettiin väkilannoitetta (10-25% kasvin typentarpeesta) päästiin varsin lähelle kontrollikäsittelyiden satotasoja. Myös pelkän LLJ-lannoitteen tuottamat satotasot olivat kuitenkin selvästi paremmat kuin Suomen keskimääräiset juurikassadot. Viljo-käsittelyillä oli selvästi positiivinen vaikutus laatutekijöihin amino-N, K ja Na vuonna 2008, mutta vuonna 2009 näiden pitoisuudet jäivät kontrollikäsittelyjen tasolle. Viljo-käsittelyiden sokeripitoisuudet olivat vuonna 2008 kontrollikäsittelyn luokkaa ja Viljo77%+NK1:n osalta kontrollia merkitsevästi paremmat. Vuoden 2009 sokeripitoisuudet olivat kaikilla koejäsenillä erinomaiset, ja käsittelyiden välillä ei ilmennyt merkitseviä eroja. Kokeiden perusteella kaliumsulfaatilla täydennetty lihaluujauho on hyvin toimiva lannoite sokerijuurikkaalla Suomen olosuhteissa, etenkin yhdistettynä väkilannoitteeseen.

Redistribution of subcellular calcium in rat liver on administration of vanadate

Mitochondria isolated from the livers of rats administered with sodium meta-, ortho-, or polyvanadate, but not vanadyl sulphate, exhibited enhanced Ca2+ — stimulated respiration and uptake of calcium. These effects were shown also by mitochondria isolated from livers perfused with polyvanadate. The concentration of acid-soluble calcium decreased significantly in the mitochondrial fraction on vanadate treatment, while that in the cytosol showed a corresponding increase. Phenoxybenzamine, an antagonist to a-adrenergic receptors, effectively inhibited vanadate-induced Ca2+ mobilization, but surgical sympathectomy was without effect. This is the first demonstration of vanadate mimicking agr-adrenergic agonists in vivo.

Electron paramagnetic resonance evidence for Jahn-Teller glasses

Single crystal E.P.R. studies of copper as a dopant in lithium potassium sulphate, lithium ammonium sulphate and lithium sodium sulphate have been carried out from room temperature down to 77K. The three Jahn-Teller (JT) systems behave very similarly to one another. The room temperature dynamic JT spectra with giso = 2·19 ± 0·01 and Aiso = ±(33 ± 4) times 10-4 cm-1 transform around 247 K to spectra characterized by randomly frozen-in axial strains with g‖ = 2·4307 ± 0·0005, g⊥ = 2·083 ± 0·001, A‖ = ±(116 ± 2) times 10-4 cm-1 and A⊥ = ∓(14 ± 4) times 10-4 cm-1. We proposed that the low temperature phase (below 247 K) of each of these systems provides an example of a Jahn-Teller glass.

Electron-Paramagnetic-Res study of LiKSO4 in phase IV below -138 degrees C

A detailed single-crystal EPR study of phase IV of lithium potassium sulphate below -138 degrees C has been carried out using NH3+, which substitutes for K+, as the paramagnetic probe. The spin-Hamiltonian parameters have been evaluated at -140 degrees C and yield an isotropic g=2.0034; (AH)XX=(AH)YY=25.3 G and (AH)ZZ=23.8 G; (AN)XX=8.1 G, (AN)YY=21.2 G and (AN)ZZ=25.9 G. In this phase there are 12 magnetically inequivalent K+ sites and their occurrence is ascribed to the loss of a c glide.

Dielectric behaviour and ferroelectricity in alums

Introduction The alum family of double salts with the general formula M1+M3+(RO4)2.12H2O where M1+ is a monovalent ion (M1+ = K, Rb, Cs, Tl, NH4, CH3NH3, NH3OH3 NH3NH2, etc.) and M3+ is a trivalent metal such as Al, Fe, Cr, V, In, Ga, etc. and R is S or Se, form an isomorphous series and their general features indicate a common cubic space group Pa3. Lipson1 showed subsequently that there exist three different structure types agr, β and γ and the structure of a particular alum is dependent on the radius of the monovalent atom. The agr structure is typical of medium sized ions, the β of the larger ones and the γ of the small Na atom.2 Ferroelectricity has been reported only in alums containing NH4, CH3NH3, NH3NH3 and NH3OH. Their hindered rotations as well as the influence of sulphate group disorder on the dielectric behaviour of alums is still not clear.3 No study of the temperature dependence of the low frequency dielectric constant of some of the alums, particularly those of Cs, Rb and Tl, have been made so The present investigation was undertaken to correlate their dielectric behaviour with their composition and structural differences. Under the same experimental conditions, methyl ammonium and ammonium alums also were studied and compared with the known data.

Isolation Of A Cytokinin-Binding Protein From Cucumis-Sativus Cotyledons

A cytokinin-binding protein which exists as monomer and dimer was isolated from cucumber (Cucumis sativus L. var Guntur) cotyledons by affinity chromatography on AH-Sepharose-pi6 Ap /s> column. The protein bound to [3H]-N6-(Δ2-isopentenyl) adenosine trialcohol. On Sephadex G-50 chromatography it gave 2 peaks corresponding to molecular weight 4000 and 8000 daltons. On sodium dodecyl sulphate-polyacrylamide gel electrophoresis, it gave only one band with an apparent molecular weight of 4000 daltons.

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

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

An SOx (x = 2, 3) sensor using ?-alumina/Na2SO4 couple

A solid-state sensor for SOx (x = 2, 3) species has been designed using ?-alumina as the solid electrolyte and Na2SO4 as the auxiliary electrode. The measured e.m.f. of the cell Pt, O?2 + SO?2 + SO?3|Na2SO4short parallel?-aluminashort parallelNa2SO4|SO?3 + SO?2 + O?2, PT in the temperature range 700 K to 1150 K agrees well with values calculated using the Nernst equation. The sodium sulphate acts both as a protective covering, preventing direct access of the gaseous SOx species to the ?-alumina electrolyte, and as an auxiliary electrode, converting chemical potentials of SOx species and O2 into an equivalent sodium potential. The open-circuit e.m.f. varies non-linearly with temperature for fixed composition of inlet gas mixtures containing SO2, O2 and Ar. The response time (t0.99) of the cell varies between 1.9 ks at 750 K and 0.06 ks at 1100 K. The e.m.f. response is faster when the partial pressure of SOx at the electrode is increased than when it is decreased.