Browsing by Subject "copper"
Now showing items 1-10 of 10
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(2022)Iron superoxide dismutase 1 (FSD1) was recently characterized as a plastidial, cytoplasmic, and nuclear enzyme with osmoprotective and antioxidant functions. However, the current knowledge on its role in oxidative stress tolerance is ambiguous. Here, we characterized the role of FSD1 in response to methyl viologen (MV)-induced oxidative stress in Arabidopsis thaliana. In accordance with the known regulation of FSD1 expression, abundance, and activity, the findings demonstrated that the antioxidant function of FSD1 depends on the availability of Cu2+ in growth media. Arabidopsis fsdl mutants showed lower capacity to decompose superoxide at low Cu2+ concentrations in the medium. Prolonged exposure to MV led to reduced ascorbate levels and higher protein carbonylation in fsdl mutants and transgenic plants lacking a plastid FSD1 pool as compared to the wild type. MV induced a rapid increase in FSD1 activity, followed by a decrease after 4 h long exposure. Genetic disruption of FSD1 negatively affected the hydrogen peroxide-decomposing ascorbate peroxidase in fsdl mutants. Chloroplastic localization of FSD1 is crucial to maintain redox homeostasis. Proteomic analysis showed that the sensitivity of fsd1 mutants to MV coincided with decreased abundances of ferredoxin and photosystem II light-harvesting complex proteins. These mutants have higher levels of chloroplastic proteases indicating an altered protein turnover in chloroplasts. Moreover, FSD1 disruption affects the abundance of proteins involved in the defense response. Collectively, the study provides evidence for the conditional antioxidative function of FSD1 and its possible role in signaling.
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(2020)Abstract Herein we present the first synthesis of bicyclo[1.1.1]pentyl (BCP) sulfoximines from the corresponding sulfides. Both BCPs and sulfoximines are bioisosteres used in medicinal chemistry and therefore desirable motifs. The access to BCP sulfides was enabled by the thiol addition to [1.1.1]propellane as published before. A broad scope with specific limitations was discovered for the sulfoximination. To diversify the sulfoximines, N-acylations and N-arylations were performed. As the N-arylation was low yielding we optimized the copper(I) catalyzed reaction. A wide range of aryl iodides could be deployed and competitive reactions showed that aryl bromides react equally fast. In a scale-up we prepared a suitable precursor for a BCP drug analogue. In this work several molecular structures could be determined by single-crystal X-ray diffraction.
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(2021)The severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) remains a severe health threat. The COVID-19 infections occurring in humans and animals render human-animal interfaces hot spots for spreading the pandemic. Lessons from the past point towards the antiviral properties of copper formulations; however, data showing the "contact-time limit" surface inhibitory efficacy of copper formulations to contain SARS-CoV-2 are limited. Here, we show the rapid inhibition of SARS-CoV-2 after only 1 and 5 min on two different surfaces containing copper-silver (Cu-Ag) nanohybrids. We characterized the nanohybrids' powder and surfaces using a series of sophisticated microscopy tools, including transmission and scanning electron microscopes (TEM and SEM) and energy-dispersive X-ray spectroscopy (EDX). We used culturing methods to demonstrate that Cu-Ag nanohybrids with high amounts of Cu (similar to 65 and 78 wt%) and lower amounts of Ag (similar to 7 and 9 wt%) inhibited SARS-CoV-2 efficiently. Collectively, the present work reveals the rapid SARS-CoV-2 surface inhibition and the promising application of such surfaces to break the SARS-CoV-2 transmission chain. For example, such applications could be invaluable within a hospital or live-stock settings, or any public place with surfaces that people frequently touch (i.e., public transportation, shopping malls, elevators, and door handles) after the precise control of different parameters and toxicity evaluations.
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(2021)We describe a mechanism-guided discovery of a synthetic methodology that enables the preparation of aromatic amides from 2-bromo-2,2-difluoroacetamides utilizing a copper-catalyzed direct arylation. Readily available and structurally simple aryl precursors such as aryl boronic acids, aryl trialkoxysilanes and dimethyl-aryl-sulfonium salts were used as the source for the aryl substituents. The scope of the reactions was tested, and the reactions were insensitive to the electronic nature of the aryl groups, as both electron-rich and electron-deficient aryls were successfully introduced. A wide range of 2-bromo-2,2-difluoroacetamides as either aliphatic or aromatic secondary or tertiary amides were also reactive under the developed conditions. The described synthetic protocols displayed excellent efficiency and were successfully utilized for the expeditious preparation of diverse aromatic amides in good-to-excellent yields. The reactions were scaled up to gram quantities.
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(2018)Background: Neuroinflammation and biometal dyshomeostasis are key pathological features of several neurodegenerative diseases, including Alzheimer's disease (AD). Inflammation and biometals are linked at the molecular level through regulation of metal buffering proteins such as the metallothioneins. Even though the molecular connections between metals and inflammation have been demonstrated, little information exists on the effect of copper modulation on brain inflammation. Methods: We demonstrate the immunomodulatory potential of the copper bis(thiosemicarbazone) complex Cu-II(atsm) in an neuroinflammatory model in vivo and describe its anti-inflammatory effects on microglia and astrocytes in vitro. Results: By using a sophisticated in vivo magnetic resonance imaging (MRI) approach, we report the efficacy of Cu-II(atsm) in reducing acute cerebrovascular inflammation caused by peripheral administration of bacterial lipopolysaccharide (LPS). Cu-II(atsm) also induced anti-inflammatory outcomes in primary microglia [significant reductions in nitric oxide (NO), monocyte chemoattractant protein 1 (MCP-1), and tumor necrosis factor (TNF)] and astrocytes [significantly reduced NO, MCP-1, and interleukin 6 (IL-6)] in vitro. These anti-inflammatory actions were associated with increased cellular copper levels and increased the neuroprotective protein metallothionein-1 (MT1) in microglia and astrocytes. Conclusion: The beneficial effects of Cu-II(atsm) on the neuroimmune system suggest copper complexes are potential therapeutics for the treatment of neuroinflammatory conditions.
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(Helsingin yliopisto, 2022)Aim of this study is to develop biogeochemical exploration methods for cobalt. Several different samples were collected from study area, analyzed, and compared to each other. This study took place at Rautio village at North Ostrobothnia and more accurately over the Jouhineva mineralization. Jouhineva is well-known high-grade cobalt-copper-gold mineralization. Elements examined in this study are cobalt, copper, arsenic, zinc, selenium, and cadmium. Samples were collected from three different study profiles from the area. From these three profiles samples collected are: soil, pine, lingonberry, birch, rowan, and juniper. Water samples were collected around the study area from every location possible. Soil samples were analyzed with four different methods: Ionic leaching, aqua regia, weak leaching and pXRF. Ionic leaching and aqua regia had both elevated concentrations of cobalt, but in different locations depending on study profile. Ionic leaching detects rising ions from the ore and therefore elevated concentrations are found at different locations compared to aqua regia. Aqua regia results proved how different orientation of study profile, direction of the ore and glacial flow can affect to the anomalies of elemental concentration. Profile-2 was oriented differently to ore and glacial flow than Profile-1, and therefore elevated concentrations of cobalt and copper were not drifted away from the ore on Profile-2 like they were on Profile-1. Aqua regia and pXRF have very similar copper, arsenic and zinc results. Pine and lingonberry turn out to be the most promising plant species applied for cobalt exploration, and rowan appears to be most suitable for copper exploration. Lower detection limit could significantly improve pine analyses as exploration method and more extensive sampling could remove some of the uncertainties about the method. Lingonberry samples have elevated concentration of copper and arsenic. Birch and juniper produced somewhat unclear results. Despite this, cobalt and copper concentrations in birch leaves were elevated when compared to concentrations found in other studies. In addition to this birch is suitable for arsenic exploration. Juniper had elevated copper concentration in the study area compared to other studies. Water samples collected from the Jouhineva area yielded concentrations of cobalt, copper and arsenic that were above the average concentration in the Kalajoki area waters. Copper and arsenic were above the average concentration of the Kalajoki area in every sample collected from the study area. Cobalt was above the average concentration in all samples that were not collected directly from the pond formed in the old test mine. Zinc concentration was below the average limit in all samples collected from the area. Zinc concentration in the water samples collected from the pond is significantly lower compared to the other samples collected from the area.
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(Helsingin yliopisto, 2019)Kivennäis- ja hivenaineet ovat lypsylehmälle välttämättömiä elintoimintojen ja tuotannon ylläpitoon. Härkäpavun siementä voidaan käyttää valkuaisen lähteenä ja koko kasvustoa säilörehuna, mutta niiden hivenainekoostumusta ei tunneta yhtä hyvin kuin rypsirouheen ja nurmisäilörehun. Tutkimuksessa verrattiin lypsylehmän kivennäis- ja hivenaineiden saantia ja sulavuutta härkäpapusäilörehusta ja härkäpavun siemenestä nurmisäilörehuun ja rypsirouheeseen. Tutkielmassa tarkasteltiin kahta koetta, jotka oli tehty Viikin opetus- ja tutkimustilalla vuosina 2014 ja 2015. Molemmissa kokeissa oli 8 Ayrshire-rotuista lypsylehmää. Kokeet toteutettiin kaksinkertaisina 4x4 latinalaisina neliöinä, joissa oli neljä ruokintaa neljänä kolmen viikon jaksona. Koeasetelmat olivat 2x2 faktoriaalisia. Ensimmäisessä kokeessa faktoreina olivat säilörehun kasvilaji (nurmi tai 1:1 nurmi+härkäpapu-kevätvehnä) ja väkirehun raakavalkuaispitoisuus (175 tai 200 g/kg ka). Toisessa kokeessa faktoreina olivat valkuaistäydennys eri lähteistä (rypsirouhe tai härkäpapu), sekä näiden osittainen korvaaminen Spirulina platensis mikrolevällä. Kokeen 2 koeruokinnat olivat isonitrogeenisiä valkuaisrehujen suhteen. Kokeessa 2 kaikissa koeruokinnoissa oli sama pitoisuus kaupallista kivennäisrehua ja kokeessa 1 kivennäislisä oli täysrehuissa. Härkäpapusäilörehuseos sisälsi enemmän kivennäisaineita, mutta vähemmän hivenaineita kuin nurmisäilörehu. Härkäpavun siemen sisälsi 70 % enemmän kuparia kuin rypsirouhe. Härkäpapusäilörehuseos lisäsi eri kivennäisaineiden saantia 1-6 %, mutta vähensi hivenaineiden, kuten raudan ja mangaanin saantia 5-7 % verrattuna nurmisäilörehuun. Härkäpavun siemen lisäsi kuparin saantia 9 %, mutta pienensi magnesiumin, rikin, raudan, mangaanin ja seleenin saanteja 2-14 % verrattuna rypsirouheeseen. Härkäpavun lisääminen ruokintaan kokoviljasäilörehuna tai kokonaisena siemenenä ei vaikuttanut kivennäis- tai hivenaineiden sulavuuteen. Härkäpapusäilörehu tai härkäpavun siemen eivät eronneet merkittävästi nurmirehusta tai rypsistä hivenaineiden lähteinä. Härkäpapu ei sisältänyt mitään kivennäis- tai hivenainetta haitallisen suurta tai hälyttävän pientä määrää.
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(2016)Sharp nanoscale tips on the metal surfaces of electrodes enhance locally applied electric fields. Strongly enhanced electric fields trigger electron field emission and atom evaporation from the apexes of nanotips. Together, these processes may explain electric discharges in the form of small local arcs observed near metal surfaces in the presence of electric fields, even in ultra-high vacuum conditions. In the present work, we investigate the stability of nanoscale tips by means of computer simulations of surface diffusion processes on copper, the main material used in high-voltage electronics. We study the stability and lifetime of thin copper (Cu) surface nanotips at different temperatures in terms of diffusion processes. For this purpose we have developed a surface kinetic Monte Carlo (KMC) model where the jump processes are described by tabulated precalculated energy barriers. We show that tall surface features with high aspect ratios can be fairly stable at room temperature. However, the stability was found to depend strongly on the temperature: 13 nm nanotips with the major axes in the <110 > crystallographic directions were found to flatten down to half of the original height in less than 100 ns at temperatures close to the melting point, whereas no significant change in the height of these nanotips was observed after 10 mu s at room temperature. Moreover, the nanotips built up along the <110 > crystallographic directions were found to be significantly more stable than those oriented in the <100 > or <111 > crystallographic directions. The proposed KMC model has been found to be well-suited for simulating atomic surface processes and was validated against molecular dynamics simulation results via the comparison of the flattening times obtained by both methods. We also note that the KMC simulations were two orders of magnitude computationally faster than the corresponding molecular dynamics calculations.
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(Helsingfors universitet, 2010)Selvitin työssäni yhdeksän vapaankaupan pötsilääkkeen sisällön koostumusta ja vaikutusta pötsissä. Vertasin valmisteiden ohjeannosten mukaisia määriä ainesosakohtaisesti niiden tarpeellisuuteen, kirjallisuudessa suositeltuihin hoitoannoksiin ja lehmän päivittäiseen saantiin rehuista. Ruokintatasoksi valittiin yksinkertaisuuden vuoksi 20 kg KA/pv, joista 12 kg KA tulee säilörehusta, 8 kg KA ohrasta ja 2 kg KA rypsirouheesta. Voimakas väkirehuruokinta tai väkirehun osuuden liian nopea lisääminen ruokinnassa altistavat pötsin happamoitumiselle. Luontaisen puskuroinnin ollessa riittämätöntä, pötsin happamuutta voidaan alentaa puskuroivilla tai alkaloivilla aineilla. Yhdeksästä valmisteesta viisi sisältää happamuutta alentavia aineita. Näistä viidestä valmisteesta kahdessa (ReCovin pötsin pH pasta, Correct pH Kombi) aineiden määrä on riittävä. Natriumbikarbonaatti (ruokasooda) on puskuri ja magnesiumoksidi on alkaloiva aine, molemmat ovat tehokkaita happamuuden alentajia. Myös hiivat alentavat pötsinesteen happamuutta. Ne vähentävät maitohapon kertymistä ja lisäävät kuitua sulattavien bakteerien määrää pötsissä. Kolmessa valmisteessa yhdeksästä on riittävästi hiivaa (Super Vetrumin -jauhe, Rumelan, Correct Pötsi-Potku). Propyleeniglykoli on tehokkaana märehtijän verensokeria kohottavana aineena tarpeellinen herumiskaudella olevan syömättömän lehmän tukihoidossa. Propyleeniglykolia on kahdessa valmisteessa (Rumex pH-pasta, Correct Pötsi-Potku). Hivenaineista seleenin on todettu lisäävän alkueläinten määrää pötsissä, ja mikrobit käyttävät sitä proteiinisynteesissään. Kobolttia tarvitaan B12-vitamiinin synteesiin. B12-vitamiinia tarvitaan märehtijän energia-aineenvaihdunnalle välttämättömässä glukoneogeneesissä. Kobolttia on riittävästi viidessä valmisteessa (ReCovin Pötsin pH-pasta, Super Vetrumin -jauhe, Rumelan, Rumex, Rumevit), seleeniä vain yhdessä (ReCovin Pötsin pH-pasta). Mikrobitoiminnan häiriössä B-vitamiinien synteesi pötsissä saattaa vähentyä. Varsinkin B1-vitamiinin eli tiamiinin puute tiaminaasin tuotannon takia happamassa pötsissä ja sen yhteys kerebrokortikaali nekroosiin on hyvin tunnettu. B3-vitamiinin eli niasiinin on todettu tehostavan pötsimikrobien proteiinisynteesiä. B-vitamiineja on lisätty riittävästi neljään valmisteeseen (Biorumin, Super Vetrumin -jauhe, Rumex, Rumevit). Tutkielmassani pohdin myös millainen olisi hyvä pötsilääke. Pötsilääkkeisiin valitsin 8 edellä mainittua hyödyllistä ainetta. Happaman pötsin hoitoon suosittelen natriumbikarbonaattia ja/tai magnesiumoksidia ja hiivaa, niiden happamuutta alentavan vaikutuksen takia. Tiamiinia (B1-vitamiini), koska siitä on happamassa pötsissä todennäköisesti puutetta, ja propyleeniglykolia tukihoidoksi energiavajeeseen. Yksinkertaisen pötsihäiriön hoitoon suosittelen hiivaa, kobolttia, seleenimetioniinia (orgaaninen seleeni) ja niasiinia (B3-vitamiini) niiden pötsimikrobistoa elvyttävän vaikutuksen takia, ja propyleeniglykolia energiavajeeseen. Yhtä tärkeänä, kuin pötsihäiriöiden lääkitsemistä, pidän niiden ennaltaehkäisyä, jossa tärkeimpiä asioita ovat nopeiden ruokinnanmuutosten välttäminen ja rehujen hyvä laatu. Lisäksi on hyvä muistaa kuivan heinän edulliset vaikutukset märehtimistä, syljen erittymistä ja pötsin liikkeitä ylläpitävänä rehuna. Riittävä syljen erittyminen on tärkeä pötsinesteen happamuutta alentava tekijä.
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(2021)Stress corrosion cracking (SCC) of oxygen-free phosphorous-alloyed copper was investigated in sulphide- and chloride-containing deoxygenated water at 90 degrees C with sulphide concentrations of 0.001 and 0.00001 M. Several intergranular defects were found in the specimen exposed to the high sulphide environment. Similar defects were not found in the low sulphide environment, where only slight corrosion on grain boundaries and slip lines occurred. Hydrogen content measurements show an increase in hydrogen uptake of the plastically deformed specimens, which is dependent on the sulphide concentration and on plastic deformation of copper. However, the highest hydrogen content was measured in friction stir welds, welded in air without shielding gas, and tested in the high sulphide environment. The embedded oxide particles in the weld metal act as local hydrogen trapping sites and selectively react with the sulphide solution. A relatively thick air-formed oxide film covers the copper canisters when deposited, which transforms into a sulphide film in the repository conditions. Thus, some of the coupon specimens were pre-oxidised. The conversion of the pre-existing Cu2O film into Cu2S film occurs quickly and the transformation is almost 100% efficient. The structure and properties of the Cu2S films, susceptibility of copper to sulphide-induced SCC and hydrogen uptake of copper in reducing, anoxic repository conditions are discussed.
