Thermal behaviour of TEGMMA copolymers obtained by photopolymerization using iron complexes

Copolymers of methyl methacrylate (MMA) and triethyleneglycol dimethacrylate (TEGDMA) obtained by photoinitiated polymerization using Fe(III) complexes were submitted to thermogravimetry (TGA) under dynamic air atmosphere and N2, and differential scanning calorimetric analysis (DSC). Thermal events were observed only between 90 - 110 ºC. Glass transitions were observed at ca. 100 ºC, followed by an exothermic peak at 170 ºC. The exothermic peak was assigned to a thermal curing process due to the presence of unreacted vinyl groups of the monomers. DSC revealed to be a useful tool to evaluate the curing completeness in this kind of material, using small amounts of sample in relatively short time.

Electrochemical study and dependence of 'transition state' in Co(II) and Ni(II) complexes with some antibiotics and cephalothin

Electrode kinetics and study of 'transition state' with applied potential in case of [M - antibiotics - cephalothin] system were reported at pH = 7.30 ± 0.01 at suitable supporting electrolyte at 25.0ºC. The M = Co or Ni and antibiotics were doxycycline, chlortetracycline, oxytetracycline, tetracycline, minocycline, amoxicillin and chloramphenicol used as primary ligands and cephalothin as secondary ligand. Kinetic parameters viz. transfer coefficient (a), degree of irreversibility (l), diffusion coefficient (D) and rate constant (k) were determined. The values of a and k varied from 0.41 to 0.59 and 2.60 X 10-3 cm s-1 to 9.67 X 10-3 cm s-1 in case of [Co - antibiotics - cephalothin] system. In case of [Ni - antibiotics - cephalothin], a and k varied from 0.41 to 0.58 and 2.34 X 10-3 cm s-1 to 9.19 X 10-3 cm s-1 respectively confirmed that transition state behaves between oxidant and reductant response to applied potential and it adjusts it self in such a way that the same is located midway between dropping mercury electrode and solution interface. The values of rate constant confirmed the quasireversible nature of electrode processes. The stability constants (logb) of complexes were also determined.

Complexes of 3,4-dimethoxybenzoic acid anion with Cu(II), Co(II), La(III), and Nd(III)

Physico-chemical properties of 3,4-dimethoxybenzoates of Co(II), Cu(II), La(III) and Nd(III) were studied. The complexes were obtained as hydrated or anhydrous polycrystalline solids with a metal ion-ligand mole ratio of 1 : 2 for divalent ions and of 1 : 3 in the case of trivalent cations. Their colours depend on the kind of central ion: pink for Co(II) complex, blue for Cu(II), white for La(III) and violet for Nd(III) complexes. The carboxylate groups in these compounds are monodentate, bidentate bridging or chelating and tridentate ligands. Their thermal decomposition was studied in the range of 293-1173 K. Hydrated complexes lose crystallization water molecules in one step and form anhydrous compounds, that next decompose to the oxides of respective metals. 3,4 - Dimethoxybenzoates of Co(II) is directly decomposed to the appropriate oxide and that of Nd(III) is also ultimately decomposed to its oxide but with the intemediate formation of Nd2O2CO3.. The magnetic moment values of 3,4-dimethoxybenzoates determined in the range of 76-303 K change from 4.22 µB to 4.61 µB for Co(II) complex , from 0.49 µB to 1.17 µB for Cu(II) complex , and from 2.69 µB to 3.15 µB for Nd(III) complex.

Stability constants and thermodynamic parameters of cadmium complexes with sulfonamides and cephapirin

Stability constant (log beta) and thermodynamic parameters of Cd2+ complexes with sulfonamide and cephapirin were determined by Polarographic technique at pH = 7.30 ± 0.01 and µ = 1.0 M KNO3 at 250°C. The sulfonamides were sulfadiazine, sulfisoxazole, sulfamethaxazole, sulfamethazine, sulfathiazole, sulfacetamide and sulfanilamide used as primary ligands and cephapirin as secondary ligand. Cd2+ formed 1:1:1, 1:2:1 and 1:1:2 complexes. The nature of electrode processes were reversible and diffusion controlled. The stability constants and thermodynamic parameters (deltaG, deltaH and deltaS) were determined. The formation of the metal complexes has been found to be spontaneous, exothermic in nature, and entropically unfavourable at higher temperature.

Study of complexes of cadmium with some L-amino acids and vitamin-C by voltammetric technique

Voltammetric technique was used to study the binary and ternary complexes of cadmium with L-amino acids and vitamin-C (L-ascorbic acid) at pH =7.30 ± 0.01, µ = 1.0M KNO3 at 25ºC and 35ºC. Cd (II) formed 1:1:1, 1:1:2 and 1:2:1 complexes with L-lysine, L-ornithine, L-threonine, L-serine, L-phenylglycine, L-phenylalanine, L-glutamic acid and L-aspartic acid used as primary ligands and L-ascorbic acid used as secondary ligand. The trend of stability constant of complexes was L-lysine < L-ornithine < L-threonine < L-serine < L-phenylglycine < L-phenylalanine < L-glutamic acid < L-aspartic acid which can be explained on the basis of size, basicity and steric hindrance of ligands. The values of stability constant (log β) varied from 2.23 to11.33 confirm that these drugs i.e. L-amino acids or in combination with L-ascorbic acid or their complexes could be used against Cd (II) toxicity. The study has been carried out at 35ºC also to determine the thermodynamic parameters such as enthalpy change (ΔH), Free energy change (ΔG) and entropy change (ΔS) respectively.

Complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III)

The complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) have been synthesized as polycrystalline hydrated solids, and characterized by elemental analysis, spectroscopy, magnetic studies and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have the following colours: violet for Nd(III), white for Gd(III) and cream for Ho(III) compounds. The carboxylate groups bind as bidentate chelating (Ho) or bridging ligands (Nd, Gd). On heating to 1173K in air the complexes decompose in several steps. At first, they dehydrate in one step to form anhydrous salts, that next decompose to the oxides of respective metals. The gaseous products of their thermal decomposition in nitrogen were also determined and the magnetic susceptibilites were measured over the temperature range of 76-303K and the magnetic moments were calculated. The results show that 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) are high-spin complexes with weak ligand fields. The solubility value in water at 293K for analysed 4-chlorophenoxyacetates is in the order of 10-4mol/dm³.

Formation of polyelectrolyte multilayers and polyelectrolyte complexes in dual polymer treatment of papermaking pulp

The goal of this study was to find a new approach to modify chemically the properties of paper by improving fiber quality. This Master’s thesis includes the multiple polymer treatment in general and themeasurement methods with which the formation of multilayers and complexes can be noticed. The treatment by an oppositely charged dual polymer system is a good approach to increase paper strength. In this work, starch, a cationic polymer, and carboxymethyl cellulose (CMC), an anionic polymer, were used step-by-step to improve paper strength. The adsorption of cationic starch and CMC on cellulose fibers were analyzed via polyelectrolyte titration. The results showed that paper strength was enhanced slightly with a layer-by-layer assembly of the polymers. However, if the washing stage, which was required for layer-by-layer assembly, was eliminated, the starch/CMC complex was deposited on fibers more efficiently, and the paper strength was improved more significantly.

Nikkelille selektiivisen kelatoivan adsorbenttimateriaalin valmistus ja tutkiminen

Metallien laajamittaisen ja runsaan käytön vuoksi nykyään on keskityttävä aikaisempaa tarkemmin metallipäästöjen estämiseen ja puhdistamiseen. Metallien puhdistamiseen jätevesistä voidaan käyttää erilaisia yksikköoperaatiomenetelmiä, mutta selektiivisempään erotukseen päästään ioninvaihto- ja adsorbenttimateriaaleilla. Työn tarkoitusena on valmistaa ja tutkia nikkeliselektiivisiä adsorbenttimateriaaleja. Lisäksi tutkimuskohteena on nikkelin ja 1,10-fenantroliinin välisen kompleksin muodostuminen eri pH-arvoilla. Selektiivisten adsorbenttimateriaalien valmistaminen onnistuu liittämällä kiinteään kantajaan ligandi. Tämän työn tapauksessa nikkelitemplaatin liittäminen kiinteään kantajaan funktionalisointivaiheessa muodostaa adsorbenttiin nikkelille spesifisen kohdan. Käytännössä spesifisyyden syntyminen ei ole itsestäänselvyys, vaan se riippuu paljon funktionalisointitavasta. Tässä työssä funktionalisointitapana olivat fysikaalinen adsorptio ja impregnointi. Nikkelin ja 1,10-fenantroliinin välisen kompleksin muodostumista tutkittiin eri pH-arvojen lisäksi neljällä eri happokonsentraatiolla. Tuloksia verrattiin sellaisen liuoksen spektriin, missä oli pelkkää nikkeliä. Tuloksista havaittiin, että komplekseja muodostuu käytännössä samalla tavalla pH:n ollessa 1–6. Vasta 5 M HNO3 alkoi heikentää kompleksien muodostumista, ja 10 M HNO3 esti kompleksien muodostumisen täysin. Adsorbenttimateriaaleja valmistettiin useita erilaisia, joihin osaan liitettiin nikkelitemplaatti ja osa jätettiin ilman templaattia. Työssä keskityttiin tutkimaan erityisesti kolmea silikasta valmistettua materiaalia, joissa vain kahdessa oli nikkelitemplaatti. Nikkelitemplaattien olemassaololla ei havaittu olevan juurikaan merkitystä nikkelin erottamiseen vesiliuoksista. Materiaaleille tehdyt regenerointikokeet osoittivat, että materiaalien toiminta ja kapasiteetti eivät olleet toivotulla tasolla.

Ammonia regeneration in nickel matte chloride leaching

Ammonia can be used as a pH controller in chloride-based metal recovery processes. In chloride conditions, ammonia reacts to ammonium chloride which can be regenerated back to ammonia with lime. Although the regeneration process itself has been known for a long time, the concentrations, non-reacting species, conditions, and even goals are different when comparing the ammonia regeneration process in different industries. The main objective of this thesis was to study the phenomena, equipment, and challenges in ammonia regeneration in the nickel process and to make a preliminary process design. The study concentrated on the regeneration and recovery units. The thesis was made by process simulation and laboratory tests using the current processes as initial information. The results were combined from all of the information obtained during the studies to provide a total process solution, which can be used as a basis when designing an ammonia regeneration process to be used in industry. In particular, it was possible to determine ammonia recovery with a stripping column and the achievement of the desired ammonia water product within the scope of this thesis. The required mass flows and process conditions were also determined. The possible challenges and solutions or further studies to overcome them were provided as well to ease the prediction and design of the ammonia regeneration process in the future. On the basis of the results of this thesis, the ammonia regeneration process can be developed further and implemented in the nickel chloride leaching process.

Probabilistic contact preferences in protein-ligand and protein-protein complexes

Modeller för intermolekulär växelvärkan utnyttjas brett inom biologin. Analys av kontakter mellan proteiner och läkemedelsforskning representerar typiska tillämpningsområden för dylika modeller. En modell som beskriver sådana molekylära växelverkningar kan utformas med hjälp av biofysisk teori, vilket tenderar att resultera i ytterst tung beräkningsbörda även för enkla tillämpningar. Ett alternativt sätt att formulera modeller är att utnyttja stora databaser som innehåller strukturmätningar gjorda med hjälp av till exempel röntgendiffraktion. Då man använder sig av empiriska mätdata direkt, möjliggör en statistisk modell att osäkerheten och inexaktheten i datat tas till hänsyn på ett adekvat sätt, samtidigt som beräkningsbördan håller sig på en rimligare nivå jämfört med kvantmekaniska metoder som i princip borde ge de optimala resultaten. I avhandlingen utvecklades en 3D modell för numerisk undersökning av intermolekulär växelverkan baserad på Bayesiansk statistik. Modellens syfte är att åstadkomma prognoser för det hurdana eller vilka molekylstrukturer prefereras i en given kontext, d.v.s. är mer sannolika inom ramen för interaktion. Modellen testades i essentiella molekyläromgivningar - en liten molekyl vid sin bindningsplats hos ett protein och en gränsyta mellan proteinerna i ett komplex. De erhållna numeriska resultaten motsvarar väl experimentella resultat som tidigare rapporterats i litteraturen, exempelvis kvalitativa bindningsaffiniteter och kemisk kännedom av vissa aminosyrors rumsliga förmågor att utgöra bindningar. I avhandlingen gjordes ytterligare preliminära tester av den statistiska ansatsen för modellering av den centrala molekylära strukturella anpassningsbarheten. I praktiken är den utvecklade modellen ämnad som ett led i en mer omfattande analysmetod, så som en s.k. farmakofor modell. Molekyylivuorovaikutusten mallintamista hyödynnetään laajasti biologisten kysymysten tarkastelussa. Tyypillisiä esimerkkejä sovelluskohteista ovat proteiinien väliset kontaktit ja lääkesuunnittelu. Vuorovaikutuksia kuvaavan mallin lähtökohta voi olla molekyyleihin liittyvä teoria, jolloin soveltamiseen liittyvä laskenta saattaa olla erityisen raskasta, tai suuri havaintojoukko joka on saatu aikaan esimerkiksi mittaamalla rakenteita röntgendiffraktio menetelmällä. Tilastollinen malli mahdollistaa havaintoaineistossa olevan epätarkkuuden ja epävarmuuden huomioimisen, samalla pitäen laskennallisen kuorman pienempänä verrattuna periaatteessa parhaan tuloksen antavaan kvanttimekaaniseen mallinnukseen. Väitöstyössä kehitettiin bayesiläiseen tilastotieteeseen perustuva 3D malli molekyylien välisten vuorovaikutusten laskennalliseen tarkasteluun. Mallin tehtävä on tuottaa ennusteita sen suhteen, minkä tai millaisten molekyylirakenteiden väliset kompleksit ovat etusijalla, toisin sanoen todennäköisempiä, vuorovaikutustilanteessa. Työssä kehitetyn menetelmän toimivuutta testattiin käyttötarkoituksen suhteen olennaisissa molekyyliympäristöissä - pieni molekyyli sitoutumiskohdassaan proteiinissa sekä rajapinta kahden proteiinin välilllä proteiinikompleksissa. Saadut laskennalliset tulokset vastasivat hyvin vertailuun käytettyjä kirjallisuudesta saatuja kokeellisia tuloksia, kuten laadullisia sitoutumisaffiniteetteja, sekä kemiallista tietoa esimerkiksi tiettyjen aminohappojen avaruudellisesta sidoksenmuodostuksesta. Väitöstyössä myös alustavasti testattiin tilastollista lähestymistapaa tärkeän molekyylien rakenteellisen mukautuvuuden mallintamiseen. Käytännössä malli on tarkoitettu osaksi jotakin laajempaa analyysimenetelmää, kuten farmakoforimallia.

Arc fusion of self-fluxed nickel alloys

Self-fluxed nickel alloys are usually flame fused after thermal spraying. However, due to the practical aspects of high temperatures reached during flame fusing, large structures such as the hydraulic turbines for power generation, can not be efficiently coated. An alternative is to fuse the sprayed coating with a gas tungsten electric arc. In this case, heating is much more intensive and substrate temperature during and after the fusing operation is much lower, thus reducing the possibility that any problem will occur. In this work, coatings of self-fluxed nickel alloy fused by flame and gas tungsten arc were evaluated as protection of hydraulic turbines against cavitational damage. Several tests were performed, including the ASTM ultrasonically vibration-induced cavitation, optical and scanning electronic microscopic metallography, and hardness tests. The results showed that the arc-fused coating presented better cavitation damage resistance, probably due to its finer microstructure. A field application of this new technique is also described. A self-fluxed Ni alloy was flame sprayed in critical regions of Francis-type hydraulic turbine blades and fused by a gas tungsten arc after spraying. The blades will be inspected during the next two years.

Structural studies and in vivo characterisation of Oct4:PORE and Oct4/Sox2:UTF1 complexes

Monikykyiset kantasolut pystyvät erilaistumaan alkion kehityksen aikana miksi tahansa kehittyvän eläimen kudokseksi. Alkion kehitystä on tutkittu vuosikymmeniä ja ensimmäisen kerran kantasoluja viljeltiin 1980-luvulla. Noin vuosikymmen myöhemmin kloonattiin ensimmäinen nisäkäs, Dolly-lammas, mikä oli läpimurto perimän kloonauksessa. Vajaa kymmenen vuotta sitten japanilaiset tutkijat pystyivät ensimmäisen kerran tuottamaan indusoituja monikykyisiä kantasoluja. Nämä kantasolut tuotettiin ilmentämällä neljää geeniä, jotka uudelleenohjelmoivat erilaistuneet solut takaisin kantasoluiksi. Geenien ilmentymistä säätelevä ja DNA:han sitoutuvan proteiinin Oct4:n on todettu olevan tärkeä tekijä uudelleenohjelmissa. Oct4 kuuluu transkriptiotekijäperheeseen, joka säätelee geenien ilmentymistä kantasoluissa. Tässä työssä kiteytin Oct4-proteiinin sen kohde-DNA:n kanssa sekä tutkin sen sitoutumista ja atomitason rakennetta röntgensädekristallografian avulla. Tutkimuksessamme paljastui useita Oct4:n atomitason rakenteellisia ominaisuuksia, jotka selittävät sen säätelymekanismeja kantasoluissa.

2-(aminometyyli)pyridiini ligandin kompleksoituminen nikkelin kanssa eri liuottimissa

Kandidaatintyön tavoitteena oli tutkia 2-(aminometyyli)pyridiini ligandin kompleksoitumista nikkeli(II) ionin kanssa vesiliuoksissa ja eri orgaanisissa liuotinseoksissa. Työ tehtiin osana laajempaa tutkimusta, jossa pyritään määrittämään nikkelille spesifisiä erotusmateriaaleja ion imprinting tekniikkaa hyväksikäyttäen. Koesarjat sekä näihin liittyvä mittaukset suoritettiin kaikki huoneen lämmössä sekä normaalissa ilman paineessa. Koesarjojen liuosfaaseista määritettiin UV/Vis spektrofotometrisesti spektrit, joiden perusteella piirrettiin Job Plot kuvaajat. Kuvaajien havaittiin vastaavan aikaisemmissa tutkimuksissa määritettyjä kuvaajia sekä matemaattisesti laskettuja huippuarvoja. Saostuneiden kiintoaineiden koostumukset määritettiin XRD ja IR mittauksilla. Tuloksien perusteella todettiin 1:2 kompleksin saostuvan lähes poikkeuksetta kaikista saostuneista näytteistä. Mittaustuloksista johtopäätöksinä voidaan todeta liuotinseoksien ja veden määrän vaikuttavan muodostuneen kompleksin kiderakenteeseen, mutta ei saostuvaan kompleksiin.

Precipitated immune complexes of IgM induce the generation of reactive oxygen species by rabbit polymorphonuclear leucocytes

We report that immune complexes of IgM (ICIgM) antibodies and ovalbumin in the form of a precipitate from the equivalence zone induce the generation of reactive oxygen species by rabbit blood polymorphonuclear leucocytes (PMN), as measured by the chemiluminescence (CL) production in the presence of luminol. The kinetics of CL generation induced by ICIgM is quite different from that induced by precipitated immune complexes of IgG (ICIgG): the maximum rate of CL production for ICIgM occurs around 14 min, whereas for ICIgG it occurs about 5 min after incubation with the cells. Also the triggering of the process requires a higher concentration of ICIgM than of ICIgG. Evidence is presented that these effects are not mediated by interaction of the antigen (ovalbumin) with the cell, since immune precipitates of ovalbumin and the F(ab')2 fragment had no effect. Our observations that precipitated ICIgM can also be an effective stimulus for CL generation and thus for O2- production reveal a new functional capability of PMN. These results may have implications for the understanding of the participation of ICIgM (as well as of ICIgG) in inflammatory reactions mediated by PMN in immune complex diseases, and in the mechanisms of defense against microbes and other non-self agents.

The role of complement in the modulation by fluid-phase IgG of the production of reactive oxygen species by polymorphonuclear leukocytes stimulated with IgG immune complexes

The production of reactive oxygen species (ROS) by polymorphonuclear leukocytes (PMN) can be induced by immune complexes and is an important component of phagocytosis in the killing of microorganisms, but can also be involved in inflammatory reactions when immune complexes are deposited in tissues. We have observed that fluid-phase IgG can inhibit the generation of ROS by rabbit PMN stimulated with precipitated immune complexes of IgG (ICIgG) in a dose-dependent manner, acting as a modulatory factor in the range of physiological IgG concentrations. This inhibitory effect is compatible with the known affinity (Kd) of monomeric IgG for the receptors involved (FcRII and FcRIII). The presence of complement components in the immune complexes results in a higher stimulation of ROS production. In this case, however, there is no inhibition by fluid-phase IgG. The effect of complement is strongly dependent on the presence of divalent cations (Ca2+ or Mg2+) in the medium, whereas the stimulation of ICIgG (without complement) does not depend on these cations. We have obtained some evidence indicating that iC3b should be the component involved in the effect of complement through interaction with the CR3 receptor. The absence of the inhibitory effect of fluid-phase IgG in ROS production when complement is present in the immune complex shows that complement may be important in vivo not only in the production of chemotactic factors for PMN, but also in the next phase of the process, i.e., the generation of ROS.