Predictors of restenosis after percutaneous coronary intervention using bare-metal stents: a comparison between patients with and without dysglycemia

The objective of this study was to identify intravascular ultrasound (IVUS), angiographic and metabolic parameters related to restenosis in patients with dysglycemia. Seventy consecutive patients (77 lesions) selected according to inclusion and exclusion criteria were evaluated by the oral glucose tolerance test and the determination of insulinemia after a successful percutaneous coronary intervention (PCI) with a bare-metal stent. The degree of insulin resistance was calculated by the homeostasis model assessment of insulin resistance (HOMA-IR). Six-month IVUS and angiogram follow-up were performed. Thirty-nine patients (55.7%) had dysglycemia. The restenosis rate in the dysglycemic group was 37.2 vs 23.5% in the euglycemic group (P = 0.299). The predictors of restenosis using bivariate analysis were reference vessel diameter (RVD): £2.93 mm (RR = 0.54; 95%CI = 0.05-0.78; P = 0.048), stent area (SA): <8.91 mm² (RR = 0.66; 95%CI = 0.24-0.85; P = 0.006), stent volume (SV): <119.75 mm³ (RR = 0.74; 95%CI = 0.38-0.89; P = 0.0005), HOMA-IR: >2.063 (RR = 0.44; 95%CI = 0.14-0.64; P = 0.027), and fasting plasma glucose (FPG): ≤108.8 mg/dL (RR = 0.53; 95%CI = 0.13-0.75; P = 0.046). SV was an independent predictor of restenosis by multivariable analysis. Dysglycemia is a common clinical condition in patients submitted to PCI. The degree of insulin resistance, FPG, RVD, SA, and SV were correlated with restenosis. SV was inversely correlated with an independent predictor of restenosis in patients treated with a bare-metal stent.

Low-intensity red and infrared laser effects at high fluences on Escherichia coli cultures

Semiconductor laser devices are readily available and practical radiation sources providing wavelength tenability and high monochromaticity. Low-intensity red and near-infrared lasers are considered safe for use in clinical applications. However, adverse effects can occur via free radical generation, and the biological effects of these lasers from unusually high fluences or high doses have not yet been evaluated. Here, we evaluated the survival, filamentation induction and morphology of Escherichia coli cells deficient in repair of oxidative DNA lesions when exposed to low-intensity red and infrared lasers at unusually high fluences. Cultures of wild-type (AB1157), endonuclease III-deficient (JW1625-1), and endonuclease IV-deficient (JW2146-1) E. coli, in exponential and stationary growth phases, were exposed to red and infrared lasers (0, 250, 500, and 1000 J/cm2) to evaluate their survival rates, filamentation phenotype induction and cell morphologies. The results showed that low-intensity red and infrared lasers at high fluences are lethal, induce a filamentation phenotype, and alter the morphology of the E. coli cells. Low-intensity red and infrared lasers have potential to induce adverse effects on cells, whether used at unusually high fluences, or at high doses. Hence, there is a need to reinforce the importance of accurate dosimetry in therapeutic protocols.

Weldability of powder bed fusion fabricated stainless steel 316L sheets to cold rolled sheet metal

Weldability of powder bed fusion (PBF) fabricated components has come to discussion in past two years due to resent developments in the PBF technology and limited size of the machines used in the fabrication process. This study concentrated on effects of energy input of welding on mechanical properties and microstructural features of welds between PBF fabricated stainless steel 316L sheets and cold rolled sheet metal of same composition by the means of destructive testing and microscopic analysis. Optical fiber diameter, laser power and welding speed were varied during the experiments that were executed following one variable at a time (OVAT) method. One of the problems of welded PBF fabricated components has been lower elongations at break comparing to conventionally manufactured components. Decreasing energy input of the laser keyhole welding decreased elongations at break of the welded specimens. Ultimate tensile strengths were not affected significantly by the energy input of the welding, but fracturing of the specimens welded using high energy input occurred from the weld metal. Fracturing of the lower energy input welds occurred from the PBF fabricated base metal. Energy input was found to be critical factor for mechanical properties of the welds. Multioriented grain growth and formation of neck at fusion zone boundary on the cold rolled side of the weld was detected and suspected to be result from weld pool flows caused by differences in molten weld pool behaviour between the PBF fabricated and cold rolled sides of the welds.

The role of metal ions in selective and sustainable processes

Sustainability and recycling are core values in today’s industrial operations. New materials, products and processes need to be designed in such a way as to consume fewer of the diminishing resources we have available and to put as little strain on the environment as possible. An integral part of this is cleaning and recycling. New processes are to be designed to improve the efficiency in this aspect. Wastewater, including municipal wastewaters, is treated in several steps including chemical and mechanical cleaning of waters. Well-cleaned water can be recycled and reused. Clean water for everyone is one of the greatest challenges we are facing today. Ferric sulphate, made by oxidation from ferrous sulphate, is used in water purification. The oxidation of ferrous sulphate, FeSO4, to ferric sulphate in acidic aqueous solutions of H2SO4 over finely dispersed active carbon particles was studied in a vigorously stirred batch reactor. Molecular oxygen was used as the oxidation agent and several catalysts were screened: active carbon, active carbon impregnated with Pt, Rh, Pd and Ru. Both active carbon and noble metal-active carbon catalysts enhanced the oxidation rate considerably. The order of the noble metals according to the effect was: Pt >> Rh > Pd, Ru. By the use of catalysts, the production capacities of existing oxidation units can be considerably increased. Good coagulants have a high charge on a long polymer chain effectively capturing dirty particles of the opposite charge. Analysis of the reaction product indicated that it is possible to obtain polymeric iron-based products with good coagulation properties. Systematic kinetic experiments were carried out at the temperature and pressure ranges of 60B100°C and 4B10 bar, respectively. The results revealed that both non-catalytic and catalytic oxidation of Fe2+ to Fe3+ take place simultaneously. The experimental data were fitted to rate equations, which were based on a plausible reaction mechanism: adsorption of dissolved oxygen on active carbon, electron transfer from Fe2+ ions to adsorbed oxygen and formation of surface hydroxyls. A comparison of the Fe2+ concentrations predicted by the kinetic model with the experimentally observed concentrations indicated that the mechanistic rate equations were able to describe the intrinsic oxidation kinetics of Fe2+ over active carbon and active carbon-noble metal catalysts. Engineering aspects were closely considered and effort was directed to utilizing existing equipment in the production of the new coagulant. Ferrous sulphate can be catalytically oxidized to produce a novel long-chained polymeric iron-based flocculent in an easy and affordable way in existing facilities. The results can be used for modelling the reactors and for scale-up. Ferric iron (Fe3+) was successfully applied for the dissolution of sphalerite. Sphalerite contains indium, gallium and germanium, among others, and the application can promote their recovery. The understanding of the reduction process of ferric to ferrous iron can be used to develop further the understanding of the dissolution mechanisms and oxidation of ferrous sulphate. Indium, gallium and germanium face an ever-increasing demand in the electronics industry, among others. The supply is, however, very limited. The fact that most part of the material is obtained through secondary production means that real production quota depends on the primary material production. This also sets the pricing. The primary production material is in most cases zinc and aluminium. Recycling of scrap material and the utilization of industrial waste, containing indium, gallium and geranium, is a necessity without real options. As a part of this study plausible methods for the recovery of indium, gallium and germanium have been studied. The results were encouraging and provided information about the precipitation of these valuables from highly acidic solutions. Indium and gallium were separated from acidic sulphuric acid solutions by precipitation with basic sulphates such as alunite or they were precipitated as basic sulphates of their own as galliunite and indiunite. Germanium may precipitate as a basic sulphate of a mixed composition. The precipitation is rapid and the selectivity is good. When the solutions contain both indium and gallium then the results show that gallium should be separated before indium to achieve a better selectivity. Germanium was separated from highly acidic sulphuric acid solutions containing other metals as well by precipitating with tannic acid. This is a highly selective method. According to the study other commonly found metals in the solution do not affect germanium precipitation. The reduction of ferric iron to ferrous, the precipitation of indium, gallium and germanium, and the dissolution of the raw materials are strongly depending on temperature and pH. The temperature and pH effect were studied and which contributed to the understanding and design of the different process steps. Increased temperature and reduced pH improve the reduction rate. Finally, the gained understanding in the studied areas can be employed to develop better industrial processes not only on a large scale but also increasingly on a smaller scale. The small amounts of indium, gallium and germanium may favour smaller and more locally bound recovery.

Metal-Ion-Binding Oligonucleotides: High-Affinity Probes for Nucleic Acid Sequences

Small non-coding RNAs have numerous biological functions in cell and are divided into different classes such as: microRNA, snoRNA, snRNA and siRNA. MicroRNA (miRNA) is the most studied non-coding RNA to date and is found in plants, animals and some viruses. miRNA with short sequences is involved in suppressing translation of target genes by binding to their mRNA post-transcriptionally and silencing it. Their function besides silencing of the viral gene, can be oncogenic and therefore the cause of cancer. Hence, their roles are highlighted in human diseases, which increases the interest in using them as biomarkers and drug targets. One of the major problems to overcome is recognition of miRNA. Owing to a stable hairpin structure, chain invasion by conventional Watson-Crick base-pairing is difficult. One way to enhance the hybridization is exploitation of metal-ion mediated base-pairing, i. e. oligonucleotide probes that tightly bind a metal ions and are able to form a coordinative bonds between modified and natural nucleobases. This kind of metallo basepairs containing short modified oligonucleotides can also be useful for recognition of other RNA sequences containing hairpin-like structural motives, such as the TAR sequence of HIV. In addition, metal-ion-binding oligonucleotides will undoubtedly find applications in DNA-based nanotechnology. In this study, the 3,5-dimethylpyrazol-1-yl substituted purine derivatives were successfully incorporated within oligonucleotides, into either a terminal or non-terminal position. Among all of the modified oligonucleotides studied, a 2-(3,5-dimethylpyrazol-1-yl)-6-oxopurine base containing oligonucleotide was observed to bind most efficiently to their unmodified complementary sequences in the presence of both Cu2+ or Zn2+. The oligonucleotide incorporating 2,6-bis(3,5-dimethylpyrazol-1-yl)purine base also markedly increased the stability of duplexes in the presence of Cu2+ without losing the selectivity.

Bearing-spesific complications of total hip arthroplasty: characterization and treatment

Hip resurfacing arthroplasty (HRA) and large head metal-on-metal total arthroplasty (LDH MoM THA) gained popularity during the last decade. Adverse reaction to metal debris (ARMD) is a unique complication of metal bearings. ARMD is a complex reaction caused by metal debris from metal-on- metal bearing surfaces and from trunnion corrosion of modular junctions. We analyzed survivorship of 8059 LDH MoM THAs based on data of the Finnish Arthroplasty Register. We found relatively high short-term survivorship for some LDH MoM THAs, but there were remarkable differences between the devices studied. After some alarming reports of failing MoM THAs, we studied the first 80 patients who had received a ReCap-M2a-Magnum implant at our institution and evaluated the prevalence of ARMD. We found a high prevalence of pseudotumors, and, because of this, we discontinued the use of MoM bearings and followed up all patients with a MoM THA. Bone loss due infection, osteolysis or fracture poses a great challenge for reconstructive and fracture surgery. Onlay allografting for both revision and fracture surgery provides mechanical stability and increases bone stock. Bone loss and implant stability must be assessed preoperatively and adequately classified; this provides guidelines for the operative treatment of periprosthetic fractures and revision THA. In our studies on structural allografts union rates were high, although the rates of infections and dislocations were marked. In summary, early results of the use of LDH MoM devices were encouraging. However, the survival of the LDH MoMs varied. The prevalence of adverse reaction to metal debris was high after application of the ReCap-Magnum THA. New implants should be introduced carefully and under close surveillance by University clinics and arthroplasty registers.

Aikaerotteisesti fluoresenssia mittaavan reaaliaikaisen PCR-laitteen kehitys

Kvantitatiivinen reaaliaikainen polymeraasiketjureaktio (engl. polymerase chain reaction, PCR) on osoittautunut käyttäjäystävällisimmäksi menetelmäksi nukleiinihapposekvenssien kvantitoimisessa. Tätä menetelmää voidaan herkistää pienempien DNA-pitoisuuksien havaitsemiseen käyttämällä hyväksi aikaerotteista fluorometriaa (engl. time-resolved fluorometry, TRF) ja luminoivia lantanidileimoja, joiden fluoresenssin pitkän eliniän ansiosta emission mittaus voidaan suorittaa vasta hetki virittävän valopulssin jälkeen, jolloin lyhytikäinen taustasäteily ehtii sammua. Tuloksena saadaan korkea signaali-taustasuhde. Tämän diplomityön tarkoituksena oli rakentaa TRF:än pystyvä reaaliaikainen PCR-laite, sillä tällaista laitetta ei ole markkinoilla tarjolla. Laite rakennettiin kehittämällä lämpökierrätin ja yhdistämällä se valmiiseen TRF:än kykenevään mittapäähän. Mittapään ja lämpökierrättimen hallitsemiseksi kehitettiin myös tietokoneohjelma. Valon tuottamiseksi ja mittaamiseksi haluttiin käyttää edullisia komponentteja, joten työssä käytettiin valmiin mittapään optiikkaa, jossa viritys tapahtuu hohtodiodilla (engl. light-emitting diode, LED) ja lantanidileiman emission mittaus fotodiodilla (engl. photodiode, PD) tai valomonistinputkella (engl. photomultiplier tube, PMT). Myös mittapään suorituskykyä tutkittiin. Työtä varten kehitettiin lämpökierrätin, joka koostui Peltier-elementillä lämmitettävästä PCR-putkitelineestä ja lämpökannesta. Mittalaitteen suorituskyvyn tutkimiseen käytettiin kelaattikomplementaatioon perustuvaa PCR-tuotteen havaitsemismenetelmää. Kelaattikomplementaatio perustuu kahteen erilliseen oligonukleotidimolekyyliin, joista toiseen on sidottu lantanidi-ioni ja toiseen valoa absorboiva ligandirakenne, jotka yhdessä muodostavat fluoresoivan kokonaisuuden. Kehitetyn lämpökierrättimen todettiin olevan tarpeeksi tarkka sekä tehokas ja sen lämmitys- ja jäähdytysnopeuden maksimeiksi saatiin 2,6 °C/sekunti. Detektorina käytetyn PD:n ei todettu olevan tarpeeksi herkkä emission havainnoimiseksi ja se korvattiin laitteessa PMT:llä. Käytetyllä PCR-määrityksellä kynnyssykleiksi (engl. threshold cycle, Ct) sekä kehitetylle että referenssilaitteelle saatiin 28,4 käyttämällä samaa 100 000 kopion DNA:n aloitusmäärää. Työssä osoitettiin, että on mahdollista kehittää edullisia komponentteja käyttävä, TRF:än pystyvä, reaaliaikainen PCR-laite, joka kykenee vastaavaan Ct-arvoon kuin vertailulaite. PD:n herkkyys ei kuitenkaan riittänyt. Tulokset olivat lupaavia, sillä LED- ja PD-teknologiat kehittyvät ja markkinoille on tullut myös muita komponentteja, joiden avulla on tulevaisuudessa mahdollista kehittää vielä herkempi laite.

Recognition of nucleic acids by metal ion complexes

Metal-ion-mediated base-pairing of nucleic acids has attracted considerable attention during the past decade, since it offers means to expand the genetic code by artificial base-pairs, to create predesigned molecular architecture by metal-ion-mediated inter- or intra-strand cross-links, or to convert double stranded DNA to a nano-scale wire. Such applications largely depend on the presence of a modified nucleobase in both strands engaged in the duplex formation. Hybridization of metal-ion-binding oligonucleotide analogs with natural nucleic acid sequences has received much less attention in spite of obvious applications. While the natural oligonucleotides hybridize with high selectivity, their affinity for complementary sequences is inadequate for a number of applications. In the case of DNA, for example, more than 10 consecutive Watson-Crick base pairs are required for a stable duplex at room temperature, making targeting of sequences shorter than this challenging. For example, many types of cancer exhibit distinctive profiles of oncogenic miRNA, the diagnostics of which is, however, difficult owing to the presence of only short single stranded loop structures. Metallo-oligonucleotides, with their superior affinity towards their natural complements, would offer a way to overcome the low stability of short duplexes. In this study a number of metal-ion-binding surrogate nucleosides were prepared and their interaction with nucleoside 5´-monophosphates (NMPs) has been investigated by 1H NMR spectroscopy. To find metal ion complexes that could discriminate between natural nucleobases upon double helix formation, glycol nucleic acid (GNA) sequences carrying a PdII ion with vacant coordination sites at a predetermined position were synthesized and their affinity to complementary as well as mismatched counterparts quantified by UV-melting measurements.

Pulssitettu laserablaatio mikrofluidisten kanavistojen sarjatuotantomenetelmänä

Puolijohteiden yleistyttyä vuodesta 1948 alkaen, ovat elektroniset laitteet pienentyneet jatkuvasti tehojen kuitenkin kasvaessa. Kasvaneet tehotiheydet kuitenkin vaikeuttavat laitesuunnittelua, sillä puoljohdekomponenttien suorituskyvylle ja eliniälle on oleellista lämpötilojen ja lämpötilavaihteluiden minimointi. Perinteisen ilmajäähdytyksen lähestyessä rajojaan niin kokonaistehon kuin järkevän energiatehokkuudenkin suhteen, on parhaaksi seuraavaksi teknologiaksi ennustettu kaksifaasijäähdytystä, jonka suorituskyky ja energiatehokkuus ovat vaaditulla tasolla. Kaksifaasijäähdytyksen optimaaliselle toiminnalle tärkeää on hyvin suunniteltu ja tarkasti valmistettu lämmönsiirtopinta, jota kutsutaan mikrokanavistoksi. Pulssitettu laserkaiverrus on edistynyt valmistustekniikka, jonka tarkkuus ja luotettavuus sopisivat mikrokanavistojen valmistamiseen. Laserkaiverruksella saavutettavat lopputulokset vaihtelevat kuitenkin materiaalista riippuen ja kupari – jota käytetään yleisesti lämmönjohteena – on eräs huonoimmin lasertyöstöön reagoivista materiaaleista ja siksi on oleellista selvittää laser-kaiverruksen toimivuutta kuparisten mikrokanavistojen valmistuksessa. Pulssitetun laser-kaiverruksen eri variaatioista nanosekunti-luokan pulssinpituuksilla toimivat laitteet ovat jatkuvan tuotannon kannalta paras vaihtoehto niiden hyvän tuottavuuden, saatavuuden sekä kohtuullisen alkuinvestoinnin vuoksi. Käytännön kaiverruskokeiden perusteella selvisi, että menetelmä on laatunsa ja tarkkuutensa puolesta sopiva varsinaiseen tuotantoon. Kaiverruksen tehokkuus kuparia työstettäessä on kuitenkin ennakoituakin heikompi ja niin valmistus- kuin suunnitelu-prosessikin vaativat vielä jatkotutkimusta ja -kehitystä.

Metal oxides prepared through the nanocasting approach-mechanistic study, surface interactions and applications in separation

Mesoporous metal oxides are nowadays widely used in various technological applications, for instance in catalysis, biomolecular separations and drug delivery. A popular technique used to synthesize mesoporous metal oxides is the nanocasting process. Mesoporous metal oxide replicas are obtained from the impregnation of a porous template with a metal oxide precursor followed by thermal treatment and removal of the template by etching in NaOH or HF solutions. In a similar manner to the traditional casting wherein the product inherits the features of the mold, the metal oxide replicas are supposed to have an inverse structure of the starting porous template. This is however not the case, as broken or deformed particles and other structural defects have all been experienced during nanocasting experiments. Although the nanocasting technique is widely used, not all the processing steps are well understood. Questions over the fidelity of replication and morphology control are yet to be adequately answered. This work therefore attempts to answer some of these questions by elucidating the nanocasting process, pin pointing the crucial steps involved and how to harness this knowledge in making wholesome replicas which are a true replication of the starting templates. The rich surface chemistry of mesoporous metal oxides is an important reason why they are widely used in applications such as catalysis, biomolecular separation, etc. At times the surface is modified or functionalized with organic species for stability or for a particular application. In this work, nanocast metal oxides (TiO2, ZrO2 and SnO2) and SiO2 were modified with amino-containing molecules using four different approaches, namely (a) covalent bonding of 3-aminopropyltriethoxysilane (APTES), (b) adsorption of 2-aminoethyl dihydrogen phosphate (AEDP), (c) surface polymerization of aziridine and (d) adsorption of poly(ethylenimine) (PEI) through electrostatic interactions. Afterwards, the hydrolytic stability of each functionalization was investigated at pH 2 and 10 by zeta potential measurements. The modifications were successful except for the AEDP approach which was unable to produce efficient amino-modification on any of the metal oxides used. The APTES, aziridine and PEI amino-modifications were fairly stable at pH 10 for all the metal oxides tested while only AZ and PEI modified-SnO2 were stable at pH 2 after 40 h. Furthermore, the functionalized metal oxides (SiO2, Mn2O3, ZrO2 and SnO2) were packed into columns for capillary liquid chromatography (CLC) and capillary electrochromatography (CEC). Among the functionalized metal oxides, aziridinefunctionalized SiO2, (SiO2-AZ) showed good chemical stability, and was the most useful packing material in both CLC and CEC. Lastly, nanocast metal oxides were synthesized for phosphopeptide enrichment which is a technique used to enrich phosphorylated proteins in biological samples prior to mass spectrometry analysis. By using the nanocasting technique to prepare the metal oxides, the surface area was controlled within a range of 42-75 m2/g thereby enabling an objective comparison of the metal oxides. The binding characteristics of these metal oxides were compared by using samples with different levels of complexity such as synthetic peptides and cell lysates. The results show that nanocast TiO2, ZrO2, Fe2O3 and In2O3 have comparable binding characteristics. Furthermore, In2O3 which is a novel material in phosphopeptide enrichment applications performed comparably with standard TiO2 which is the benchmark for such phosphopeptide enrichment procedures. The performance of the metal oxides was explained by ranking the metal oxides according to their isoelectric points and acidity. Overall, the clarification of the nanocasting process provided in this work will aid the synthesis of metal oxides with true fidelity of replication. Also, the different applications of the metal oxides based on their surface interactions and binding characteristics show the versatility of metal oxide materials. Some of these results can form the basis from which further applications and protocols can be developed.

Geochemistry and mineralogical association of heavy metal contaminants in fine grained sediment, Welland River, Southern Ontario /

This investigation of geochemistry and mineralogy of heavy metals in fine grained (<63^m) sediment of the Welland River was imdertaken to: 1) describe metal dispersion patterns relative to a source, identify minerals forming and existing at the outfall region and relate sediment particle size to chemistry; 2) to delineate sample handling, preparation and evaluate, modify and develop analytical methods for heavy metal analysis of complex environmental samples. Ajoint project between Brock University and Geoscience Laboratories was initiated to test a contaminated site of the Welland River at the base of Atlas Speciality Steels Co. Methods were developed and utilized for particle size separation and two acid extraction techniques: 1) Partial extraction; 2) Total extraction. The mineralogical assessment identified calcite, dolomite, quartz and clays. These minerals are typical of the carbonate-shale rock basement of the Niagara Peninsula. Minerals such as, mullite and ferrocolumbite were found at the outfall region. These are not typical of the local geology and are generally associated with industrial pollutants. Partial and total extraction techniques were used to characterize the sediments based on chemical distribution, elemental behaviour and analytical differences. The majority of elements were lower in concentration in the partial extraction technique; suggesting these elements are bound in an acid extractable phase (exchangeable, organic and carbonate phases). The total extraction technique yielded higher elemental concentrations taking difficult oxides and silicates into solution. Geochemical analyses of grain size separates revealed that heavy metal (Co, Ni, V, Mn, Fe, Ba) concentrations did not increase with decreasing grain size. This is a function of the anthropogenic mill scale input into the river. The background elements (Sc, Y, Sr, Mg, Al and Ti) showed an increase in concentration to the finest grain size suggesting that it is directly related to the local mineralogy and geology. Dispersion patterns ofmetals fall into two distinct categories: 1) the heavy metals (Co, Cu, Ni, Zn, V and Cr), and 2) the background elements (Be, Sc, Y, Sr, Al and Ti). The heavy metals show a marked increase in the outfall region, while the background elements show a significant decrease at the outfall. This pattern is attributed to a "dilution effect" ofthe natural sediments by the anthropogenic mill scale sediments. Multivariant statistical analysis and correlation coefficient matrix results clearly support these results and conclusions. These results indicate the outfall region ofthe Welland River is highly contaminated with to heavy metals from the industrialized area of Welland. A short distance downstream, the metal concentrations return to baseline geochemical levels. It appears, contaminants rapidly come out of suspension and are deposited in close proximity to the source. Therefore, it is likely that dredging the sediment from the river may cause resuspension of contaminated sediments, but may not distribute the sediment as far as initially anticipated.