Browsing by Subject "OXIDATION"

Sort by: Order: Results:

Now showing items 1-20 of 76
  • Mollerup, Filip; Aumala, Ville; Parikka, Kirsti Maria; Mathieu, Yan; Brumer, Harry; Tenkanen, Tiina Maija; Master, Emma (2019)
    Copper radical alcohol oxidases belonging to auxiliary activity family 5, subfamily 2 (AA5_2) catalyze the oxidation of galactose and galactosides, as well as aliphatic alcohols. Despite their broad applied potential, so far very few AA5_2 members have been biochemically characterized. We report the recombinant production and biochemical characterization of an AA5_2 oxidase from Penicillium rubens Wisconsin 54-1255 (PruAA5_2A), which groups within an unmapped clade phylogenetically distant from those comprising AA5_2 members characterized to date. PruAA5_2 preferentially oxidized raffinose over galactose; however, its catalytic efficiency was 6.5 times higher on glycolaldehyde dimer compared to raffinose. Deep sequence analysis of characterized AA5_2 members highlighted amino acid pairs correlated to substrate range and conserved within the family. Moreover, PruAA5_2 activity spans substrate preferences previously reported for AA5 subfamily 1 and 2 members, identifying possible functional overlap across the AA5 family.
  • Barmaki, Samineh; Jokinen, Ville; Obermaier, Daniela; Blokhina, Daria; Korhonen, Matti; Ras, Robin H. A.; Vuola, Jyrki; Franssila, Sami; Kankuri, Esko (2018)
    Physiological oxygen levels within the tissue microenvironment are usually lower than 14%, in stem cell niches these levels can be as low as 0-1%. In cell cultures, such low oxygen levels are usually mimicked by altering the global culture environment either by O-2 removal (vacuum or oxygen absorption) or by N-2 supplementation for O-2 replacement. To generate a targeted cellular hypoxic microenvironment under ambient atmospheric conditions, we characterised the ability of the dissolved oxygen-depleting sodium sulfite to generate an in-liquid oxygen sink. We utilised a microfluidic design to place the cultured cells in the vertical oxygen gradient and to physically separate the cells from the liquid. We demonstrate generation of a chemical in-liquid oxygen sink that modifies the surrounding O-2 concentrations. O-2 level control in the sink-generated hypoxia gradient is achievable by varying the thickness of the polydimethylsiloxane membrane. We show that intracellular hypoxia and hypoxia response element-dependent signalling is instigated in cells exposed to the microfluidic in-liquid O-2 sink-generated hypoxia gradient. Moreover, we show that microfluidic flow controls site-specific microenvironmental kinetics of the chemical O-2 sink reaction, which enables generation of intermittent hypoxia/re-oxygenation cycles. The microfluidic O-2 sink chip targets hypoxia to the cell culture microenvironment exposed to the microfluidic channel architecture solely by depleting O-2 while other sites in the same culture well remain unaffected. Thus, responses of both hypoxic and bystander cells can be characterised. Moreover, control of microfluidic flow enables generation of intermittent hypoxia or hypoxia/re-oxygenation cycles. (C) 2018 Published by Elsevier Ltd on behalf of Acta Materialia Inc.
  • Berndt, Torsten; Scholz, Wiebke; Mentler, Bernhard; Fischer, Lukas; Herrmann, Hartmut; Kulmala, Markku; Hansel, Armin (2018)
    Hydrocarbons are emitted into the Earth's atmosphere in very large quantities by human and biogenic activities. Their atmospheric oxidation processes almost exclusively yield RO2 radicals as reactive intermediates whose atmospheric fate is not yet fully unraveled. Herein, we show that gas-phase reactions of two RO2 radicals produce accretion products composed of the carbon backbone of both reactants. The rates for accretion product formation are very high for RO2 radicals bearing functional groups, competing with those of the corresponding reactions with NO and HO2. This pathway, which has not yet been considered in the modelling of atmospheric processes, can be important, or even dominant, for the fate of RO2 radicals in all areas of the atmosphere. Moreover, the vapor pressure of the formed accretion products can be remarkably low, characterizing them as an effective source for the secondary organic aerosol.
  • Joshi, Satya P.; Pekkanen, Timo T.; Seal, Prasenjit; Timonen, Raimo S.; Eskola, Arkke J. (2021)
    The kinetics of the reaction between resonance-stabilized (CH3)(2)CCHCH2 radical (R) and O-2 has been investigated using photoionization mass spectrometry, and master equation (ME) simulations were performed to support the experimental results. The kinetic measurements of the (CH3)(2)CCHCH2 + O-2 reaction (1) were carried out at low helium bath-gas pressures (0.2-5.7 Torr) and over a wide temperature range (238-660 K). Under low temperature (238-298 K) conditions, the pressure-dependent bimolecular association reaction R + O-2 -> ROO determines kinetics, until at an intermediate temperature range (325-373 K) the ROO adduct becomes thermally unstable and increasingly dissociates back to the reactants with increasing temperature. The initial association of O-2 with (CH3)(2)CCHCH2 radical occurs on two distinct sites: terminal 1(t) and non-terminal 1(nt) sites on R, leading to the barrierless formation of ROO(t) and ROO(nt) adducts, respectively. Important for autoignition modelling of olefinic compounds, bimolecular reaction channels appear to open for the R + O-2 reaction at high temperatures (T > 500 K) and pressure-independent bimolecular rate coefficients of reaction (1) with a weak positive temperature dependence, (2.8-4.6) x 10(-15) cm(3) molecule(-1) s(-1), were measured in the temperature range of 500-660 K. At a temperature of 501 K, a product signal of reaction (1) was observed at m/z = 68, probably originating from isoprene. To explore the reaction mechanism of reaction (1), quantum chemical calculations and ME simulations were performed. According to the ME simulations, without any adjustment to energies, the most important and second most important product channels at the high temperatures are isoprene + HO2 (yield > 91%) and (2R/S)-3-methyl-1,2-epoxybut-3-ene + OH (yield < 8%). After modest adjustments to ROO(t) and ROO(nt) well-depths (similar to 0.7 kcal mol(-1) each) and barrier height for the transition state associated with the kinetically most dominant channel, R + O-2 -> isoprene + HO2 (similar to 2.2 kcal mol(-1)), the ME model was able to reproduce the experimental findings. Modified Arrhenius expressions for the kinetically important reaction channels are enclosed to facilitate the use of current results in combustion models.
  • Wilson, Samuel T.; Bange, Hermann W.; Arevalo-Martinez, Damian L.; Barnes, Jonathan; Borges, Alberto; Brown, Ian; Bullister, John L.; Burgos, Macarena; Capelle, David W.; Casso, Michael; de la Paz, Mercedes; Farias, Laura; Fenwick, Lindsay; Ferron, Sara; Garcia, Gerardo; Glockzin, Michael; Karl, David M.; Kock, Annette; Laperriere, Sarah; Law, Cliff S.; Manning, Cara C.; Marriner, Andrew; Myllykangas, Jukka-Pekka; Pohlman, John W.; Rees, Andrew P.; Santoro, Alyson E.; Tortell, Philippe D.; Upstill-Goddard, Robert C.; Wisegarver, David P.; Zhang, Gui-Ling; Rehder, Gregor (2018)
    Large-scale climatic forcing is impacting oceanic biogeochemical cycles and is expected to influence the water-column distribution of trace gases, including methane and nitrous oxide. Our ability as a scientific community to evaluate changes in the water-column inventories of methane and nitrous oxide depends largely on our capacity to obtain robust and accurate concentration measurements that can be validated across different laboratory groups. This study represents the first formal international intercomparison of oceanic methane and nitrous oxide measurements whereby participating laboratories received batches of seawater samples from the subtropical Pacific Ocean and the Baltic Sea. Additionally, compressed gas standards from the same calibration scale were distributed to the majority of participating laboratories to improve the analytical accuracy of the gas measurements. The computations used by each laboratory to derive the dissolved gas concentrations were also evaluated for inconsistencies (e.g., pressure and temperature corrections, solubility constants). The results from the intercomparison and intercalibration provided invaluable insights into methane and nitrous oxide measurements. It was observed that analyses of seawater samples with the lowest concentrations of methane and nitrous oxide had the lowest precisions. In comparison, while the analytical precision for samples with the highest concentrations of trace gases was better, the variability between the different laboratories was higher: 36 % for methane and 27 % for nitrous oxide. In addition, the comparison of different batches of seawater samples with methane and nitrous oxide concentrations that ranged over an order of magnitude revealed the ramifications of different calibration procedures for each trace gas. Finally, this study builds upon the intercomparison results to develop recommendations for improving oceanic methane and nitrous oxide measurements, with the aim of precluding future analytical discrepancies between laboratories.
  • Collins, Scott; Hasan, Galib; Joshi, Anuj; McIndoe, J. Scott; Linnolahti, Mikko (2021)
    Density functional theory calculations on neutral sheet models for methylaluminoxane (MAO) indicate that these structures, containing 5-coordinate and 4-coordinate Al, are likely precursors to ion-pairs seen during the hydrolysis of trimethylaluminum (Me3Al) in the presence of donors such as octamethyltrisiloxane (OMTS). Ionization by both methide ([Me](-)) and [Me2Al](+) abstraction, involving this donor, were studied by polarizable continuum model calculations in fluorobenzene (PhF) and o-difluorobenzene (DFB) media. These studies suggest that low MW, 5-coordinate sheets ionize by [Me2Al](+) abstraction, while [Me](-) abstraction from Me3Al-OMTS is the likely process for higher MW 4-coordinate sheets. Further, comparison of anion stabilities per mole of aluminoxane repeat unit (MeAlO)(n), suggest that anions such as [(MeAlO)(7)(Me3Al)(4)Me](-)=[7,4](-) are especially stable compared to higher homologues, even though their neutral precursors are unstable.
  • Beaumont, Marco; Tardy, Blaise; Reyes, Guillermo; Koso, Tetyana; Schaubmayr, Elisabeth; Jusner, Paul; King, Alistair; Dagastine, Raymond; Potthast, Antje; Rojas, Orlando J.; Rosenau, Thomas (2021)
    Selective surface modification of biobased fibers affords effective individualization and functionalization into nanomaterials, as exemplified by the TEMPO-mediated oxidation. However, such a route leads to changes of the native surface chemistry, affecting interparticle interactions and limiting the development of potential supermaterials. Here we introduce a methodology to extract elementary cellulose fibrils by treatment of biomass with N-succinylimidazole, achieving regioselective surface modification of C6-OH, which can be reverted using mild post-treatments. No polymer degradation, cross-linking, nor changes in crystallinity occur under the mild processing conditions, yielding cellulose nanofibrils bearing carboxyl moieties, which can be removed by saponification. The latter offers a significant opportunity in the reconstitution of the chemical and structural interfaces associated with the native states. Consequently, 3D structuring of native elementary cellulose nanofibrils is made possible with the same supramolecular features as the biosynthesized fibers, which is required to unlock the full potential of cellulose as a sustainable building block.
  • Iivonen, Tomi; Heikkilä, Mikko J.; Popov, Georgi; Nieminen, Heta-Elisa; Kaipio, Mikko; Kemell, Marianna; Mattinen, Miika; Meinander, Kristoffer; Mizohata, Kenichiro; Räisänen, Jyrki; Ritala, Mikko; Leskelä, Markku (2019)
    Herein, we report an atomic layer deposition (ALD) process for Cu2O thin films using copper(II) acetate [Cu(OAc)(2)] and water vapor as precursors. This precursor combination enables the deposition of phase-pure, polycrystalline, and impurity-free Cu2O thin films at temperatures of 180-220 degrees C. The deposition of Cu(I) oxide films from a Cu(II) precursor without the use of a reducing agent is explained by the thermally induced reduction of Cu(OAc)(2) to the volatile copper(I) acetate, CuOAc. In addition to the optimization of ALD process parameters and characterization of film properties, we studied the Cu2O films in the fabrication of photoconductor devices. Our proof-of-concept devices show that approx- imately 20 nm thick Cu2O films can be used for photodetection in the visible wavelength range and that the thin film photoconductors exhibit improved device characteristics in comparison to bulk Cu2O crystals.
  • Ferreira, Daniela C.; Oliveira, Mayara L.; Bioni, Thais A.; Nawaz, Haq; King, Alistair W. T.; Kilpeläinen, Ilkka; Hummel, Michael; Sixta, Herbert; El Seoud, Omar A. (2019)
    The efficiency of mixtures of ionic liquids (ILs) and molecular solvents in cellulose dissolution and derivatization depends on the structures of both components. We investigated the ILs 1-(1-butyl)-3-methylimidazolium acetate (C(4)MeImAc) and 1-(2-methoxyethyl)-3-methylimidazolium acetate (C(3)OMeImAc) and their solutions in dimethyl sulfoxide, DMSO, to assess the effect of presence of an ether linkage in the IL side-chain. Surprisingly, C(4)MeImAc-DMSO was more efficient than C(3)OMeImAc-DMSO for the dissolution and acylation of cellulose. We investigated both solvents using rheology, NMR spectroscopy, and solvatochromism. Mixtures of C(3)OMeImAc-DMSO are more viscous, less basic, and form weaker hydrogen bonds with cellobiose than C(4)MeImAc-DMSO. We attribute the lower efficiency of C(3)OMeImAc to "deactivation" of the ether oxygen and C2-(H) under bar of the imidazolium ring due to intramolecular hydrogen bonding. Using the corresponding ILs with C2-(CH3) under bar instead of C2-(H) under bar, namely, 1-butyl-2,3-dimethylimidazolium acetate (C(4)Me(2)ImAc) and 1-(2-methoxyethyl)-2,3-dimethylimidazolium acetate (C(3)OMe(2)ImAc) increased the concentration of dissolved cellulose; without noticeable effect on biopolymer reactivity.
  • Ouedrhiri, Wessal; Mechchate, Hamza; Moja, Sandrine; Mothana, Ramzi A.; Noman, Omar M.; Grafov, Andriy; Greche, Hassane (2021)
    Several studies have demonstrated the possible synergistic effect as an effective strategy to boost the bioactivity of essential oils. Using this framework, this study was conducted to effectively establish the ideal combination of six essential oils from different plants (Origanum compactum, Origanum majorana, Thymus serpyllum, Mentha spicata, Myrtus communis, and Artemisia herba-alba) that would express the best antioxidant activity. Each mixture was optimized using a mixture design approach to generate the most effective blend. The 2,2-diphenyl-1-picrylhydrazyl radical scavenging method was used as a reference method to assess the antioxidant activity. Each essential oil's composition was identified using the GC/MS method. The single essential oil activities demonstrated variable antioxidant effects, and following the mixture design approach, the optimal antioxidant blend was revealed, as two mixtures demonstrated the best antiradical activity with 79.46% obtained with the mixture of O. majorana (28%) and M. spicata (71%) and 78.8% obtained with the mixture O. compactum (64%), O. majorana (13%), and T. serpyllum (21%). This study proposes a practical way to elaborate mixtures in the search for a boosting effect that can be oriented for the food or pharmaceutical industry.
  • Li, Xuefei; Wahlroos, Outi Marjatta; Haapanala, Sami; Pumpanen, Jukka; Vasander, Harri; Ojala, Anne; Vesala, Timo; Mammarella, Ivan (2020)
    Many wetlands have been drained due to urbanization, agriculture, forestry or other purposes, which has resulted in a loss of their ecosystem services. To protect receiving waters and to achieve services such as flood control and storm water quality mitigation, new wetlands are created in urbanized areas. However, our knowledge of greenhouse gas exchange in newly created wetlands in urban areas is currently limited. In this paper we present measurements carried out at a created urban wetland in Southern Finland in the boreal climate. We conducted measurements of ecosystem CO2 flux and CH4 flux (FCH4) at the created storm water wetland Gateway in Nummela, Vihti, Southern Finland, using the eddy covariance (EC) technique. The measurements were commenced the fourth year after construction and lasted for 1 full year and two subsequent growing seasons. Besides ecosystemscale fluxes measured by the EC tower, the diffusive CO2 and CH4 fluxes from the open-water areas (FwCO(2) and FwCH(4), respectively) were modelled based on measurements of CO2 and CH4 concentration in the water. Fluxes from the vegetated areas were estimated by applying a simple mixing model using the above-mentioned fluxes and the footprintweighted fractional area. The half-hourly footprint-weighted contribution of diffusive fluxes from open water ranged from 0% to 25.5% in 2013. The annual net ecosystem exchange (NEE) of the studied wetland was 8.0 g C-CO2 m(-2) yr(-1), with the 95% confidence interval between 18:9 and 34.9 g C-CO2 m(-2) yr(-1), and FCH4 was 3.9 g C-CH4 m(-2) yr(-1), with the 95% confidence interval between 3.75 and 4.07 g C-CH4 m(-2) yr(-1). The ecosystem sequestered CO2 during summer months (June-August), while the rest of the year it was a CO2 source. CH4 displayed strong seasonal dynamics, higher in summer and lower in winter, with a sporadic emission episode in the end of May 2013. Both CH4 and CO2 fluxes, especially those obtained from vegetated areas, exhibited strong diurnal cycles during summer with synchronized peaks around noon. The annual FwCO(2) was 297.5 g C-CO2 m(-2) yr(-1) and FwCH(4) was 1.73 g C-CH4 m(-2) yr(-1). The peak diffusive CH4 flux was 137.6 nmol C-CH4 m(-2) s(-1), which was synchronized with the FCH4. Overall, during the monitored time period, the established storm water wetland had a climate-warming effect with 0.263 kgCO(2)-eqm(-2) yr(-1) of which 89% was contributed by CH4. The radiative forcing of the open-water areas exceeded that of the vegetation areas (1.194 and 0.111 kgCO(2)-eqm(-2) yr(-1), respectively), which implies that, when considering solely the climate impact of a created wetland over a 100-year horizon, it would be more beneficial to design and establish wetlands with large patches of emergent vegetation and to limit the areas of open water to the minimum necessitated by other desired ecosystem services.
  • D'Ambro, Emma L.; Schobesberger, Siegfried; Gaston, Cassandra J.; Lopez-Hilfiker, Felipe D.; Lee, Ben H.; Liu, Jiumeng; Zelenyuk, Alla; Bell, David; Cappa, Christopher D.; Helgestad, Taylor; Li, Ziyue; Guenther, Alex; Wang, Jian; Wise, Matthew; Caylor, Ryan; Surratt, Jason D.; Riedel, Theran; Hyttinen, Noora; Salo, Vili-Taneli; Hasan, Galib; Kurten, Theo; Shilling, John E.; Thornton, Joel A. (2019)
    We present measurements utilizing the Filter Inlet for Gases and Aerosols (FIGAERO) applied to chamber measurements of isoprene-derived epoxydiol (IEPOX) reactive uptake to aqueous acidic particles and associated secondary organic aerosol (SOA) formation. Similar to recent field observations with the same instrument, we detect two molecular components desorbing from the IEPOX SOA in high abundance: C5H12O4 and C5H10O3. The thermal desorption signal of the former, presumably 2-methyltetrols, exhibits two distinct maxima, suggesting it arises from at least two different SOA components with significantly different effective volatilities. Isothermal evaporation experiments illustrate that the most abundant component giving rise to C5H12O4 is semi-volatile, undergoing nearly complete evaporation within 1 h while the second, less volatile component remains unperturbed and even increases in abundance. We thus confirm, using controlled laboratory studies, recent analyses of ambient SOA measurements showing that IEPOX SOA is of very low volatility and commonly measured IEPOX SOA tracers such as C5H12O4 and C5H10O3, presumably 2-methyltetrols and C5-alkene triols or 3-MeTHF-3,4-diols, result predominantly from thermal decomposition in the FIGAERO-CIMS. We infer that other measurement techniques using thermal desorption or prolonged heating for analysis of SOA components may also lead to reported 2-methyltetrols and C5-alkene triols or 3-MeTHF-3,4-diol structures. We further show that IEPOX SOA volatility continues to evolve via acidity-enhanced accretion chemistry on the timescale of hours, potentially involving both 2-methyltetrols and organosulfates.
  • Reyes, Guillermo; Lundahl, Meri; Alejandro-Martin, Serguei; Arteaga-Perez, Luis; Oviedo, Claudia; King, Alistair; Rojas, Orlando J. (2020)
    Hydrogels of TEMPO-oxidized nanocellulose were stabilized for dry-jet wet spinning using a shell of cellulose dissolved in 1,5-diazabicyclo[4.3.0]non-5-enium propionate ([DBNH][CO2Et]), a protic ionic liquid (PIL). Coagulation in an acidic water bath resulted in continuous core-shell filaments (CSFs) that were tough and flexible with an average dry (and wet) toughness of similar to 11 (2) MJ.m(-3) and elongation of similar to 9 (14) %. The CSF morphology, chemical composition, thermal stability, crystallinity, and bacterial activity were assessed using scanning electron microscopy with energy-dispersive X-ray spectroscopy, liquid-state nuclear magnetic resonance, Fourier transform infrared spectroscopy, thermogravimetric analysis, pyrolysis gas chromatography-mass spectrometry, wide-angle X-ray scattering, and bacterial cell culturing, respectively. The coaxial wet spinning yields PIL-free systems carrying on the surface the cellulose II polymorph, which not only enhances the toughness of the filaments but facilities their functionalization.
  • Aaen, Ragnhild; Lehtonen, Mari; Mikkonen, Kirsi S.; Syverud, Kristin (2021)
    The use of wood-derived cellulose nanofibrils (CNFs) or galactoglucomannans (GGM) for emulsion stabilization may be a way to obtain new environmentally friendly emulsifiers. Both have previously been shown to act as emulsifiers, offering physical, and in the case of GGM, oxidative stability to the emulsions. Oil-in-water emulsions were prepared using highly charged (1352 ± 5 µmol/g) CNFs prepared by TEMPO-mediated oxidation, or a coarser commercial CNF, less charged (≈ 70 µmol/g) quality (Exilva forte), and the physical emulsion stability was evaluated by use of droplet size distributions, micrographs and visual appearance. The highly charged, finely fibrillated CNFs stabilized the emulsions more effectively than the coarser, lower charged CNFs, probably due to higher electrostatic repulsions between the fibrils, and a higher surface coverage of the oil droplets due to thinner fibrils. At a constant CNF/oil ratio, the lowest CNF and oil concentration of 0.01 wt % CNFs and 5 wt % oil gave the most stable emulsion, with good stability toward coalescence, but not towards creaming. GGM (0.5 or 1.0 wt %) stabilized emulsions (5 wt % oil) showed no creaming behavior, but a clear bimodal distribution with some destabilization over the storage time of 1 month. Combinations of CNFs and GGM for stabilization of emulsions with 5 wt % oil, provided good stability towards creaming and a slower emulsion destabilization than for GGM alone. GGM could also improve the stability towards oxidation by delaying the initiation of lipid oxidation. Use of CNFs and combinations of GGM and CNFs can thus be away to obtain stable emulsions, such as mayonnaise and beverage emulsions.
  • Davodi, Fatemeh; Mühlhausen, Elisabeth; Settipani, Daniel; Rautama, Eeva-Leena; Honkanen, Ari-Pekka; Huotari, Simo; Marzun, Galina; Taskinen, Pekka; Kallio, Tanja (2019)
    Core-shell nanoparticles represent a class of materials that exhibit a variety of properties. By rationally tuning the cores and the shells in such nanoparticles (NPs), a range of materials with tailorable properties can be produced which are of interest for a wide variety of applications. Herein, experimental and theoretical approaches have been combined to show the structural transformation of NPs resulting to the formation of either NiFexCy encapsulated in ultra-thin graphene layer (NiFe@UTG) or Ni3C/FexCy@FeOx NPs with the universal one-step pulse laser ablation in liquid (PLAL) method. Analysis suggests that carbon in Ni3C is the source for the carbon shell formation, whereas the final carbon-shell thickness in the NPs originates from the difference between Ni3C and FexCy phases stability at room temperature. The ternary Ni-Fe-C phase diagram calculations reveal the competition between carbon solubility in the studied metals (Ni and Fe) and their tendency toward oxidation as the key properties to produce controlled core-shell NP materials. As an application example, the electrocatalytic hydrogen evolution current on the different NPs is measured. The electrochemical analysis of the NPs reveals that NiFe@UTG has the best performance amongst the NPs in this study in both alkaline and acidic media.
  • Heliövaara, Eeva; Liljeqvist, Henri; Muuronen, Mikko; Eronen, Aleksi; Moslova, Karina; Repo, Timo (2021)
    Development of new, environmentally benign dissolution methods for metallic gold is driven by needs in the circular economy. Gold is widely used in consumer electronics, but sustainable and selective dissolution methods for Au are scarce. Herein, we describe a quantitative dissolution of gold in organic solution under mild conditions by using hydrogen peroxide as an oxidant. In the dissolution reaction, two thiol ligands, pyridine-4-thiol and 2-mercaptobenzimidazole, work in a cooperative manner. The mechanistic investigations suggest that two pyridine-4-thiol molecules form a complex with Au-0 that can be oxidized, whereas the role of inexpensive 2-mercaptobenzimidazole is to stabilize the formed Au-I species through a ligand exchange process. Under optimized conditions, the reaction proceeds vigorously and gold dissolves quantitatively in two hours. The demonstrated ligand-exchange mechanism with two thiols allows to drastically reduce the thiol consumption and may lead to even more effective gold dissolution methods in the future.
  • Zhang, Rongjie; Xie, Hong-Bin; Ma, Fangfang; Chen, Jingwen; Iyer, Siddharth; Simon, Mario; Heinritzi, Martin; Shen, Jiali; Tham, Yee Jun; Kurten, Theo; Worsnop, Douglas R.; Kirkby, Jasper; Curtius, Joachim; Sipilä, Mikko; Kulmala, Markku; He, Xu-Cheng (2022)
    Nucleation of neutral iodine particles has recently been found to involve both iodic acid (HIO3) and iodous acid (HIO2). However, the precise role of HIO2 in iodine oxoacid nucleation remains unclear. Herein, we probe such a role by investigating the cluster formation mechanisms and kinetics of (HIO3)m(HIO2)n (m = 0-4, n = 0-4) clusters with quantum chemical calculations and atmospheric cluster dynamics modeling. When compared with HIO3, we find that HIO2 binds more strongly with HIO3 and also more strongly with HIO2. After accounting for ambient vapor concentrations, the fastest nucleation rate is predicted for mixed HIO3-HIO2 clusters rather than for pure HIO3 or HIO2 ones. Our calculations reveal that the strong binding results from HIO2 exhibiting a base behavior (accepting a proton from HIO3) and forming stronger halogen bonds. Moreover, the binding energies of (HIO3)m(HIO2)n clusters show a far more tolerant choice of growth paths when compared with the strict stoichiometry required for sulfuric acid-base nucleation. Our predicted cluster formation rates and dimer concentrations are acceptably consistent with those measured by the Cosmic Leaving Outdoor Droplets (CLOUD) experiment. This study suggests that HIO2 could facilitate the nucleation of other acids beyond HIO3 in regions where base vapors such as ammonia or amines are scarce.
  • Wallenius, Janne; Kontro, Jussi; Lyra, Christina; Kuuskeri, Jaana; Wan, Xing; Kahkonen, Mika A.; Baig, Irshad; Kamer, Paul C. J.; Sipila, Jussi; Makela, Miia R.; Nousiainen, Paula; Hilden, Kristiina (2021)
    Fungal laccases are attracting enzymes for sustainable valorization of biorefinery lignins. To improve the lignin oxidation capacity of two previously characterized laccase isoenzymes from the white-rot fungus Obba rivulosa, we mutated their substrate-binding site at T1. As a result, the pH optimum of the recombinantly produced laccase variant rOrLcc2-D206N shifted by three units towards neutral pH. O. rivulosa laccase variants with redox mediators oxidized both the dimeric lignin model compound and biorefinery poplar lignin. Significant structural changes, such as selective benzylic alpha-oxidation, were detected by nuclear magnetic resonance analysis, although no polymerization of lignin was observed by gel permeation chromatography. This suggests that especially rOrLcc2-D206N is a promising candidate for lignin-related applications.
  • Hiltunen, Arto; Ruoko, Tero-Petri; Iivonen, Tomi; Lahtonen, Kimmo; Ali-Löytty, Harri; Sarlin, Essi; Valden, Mika; Leskelä, Markku; Tkachenko, Nikolai (2018)
    Iron and titanium oxides have attracted substantial attention in photoelectrochemical water splitting applications. However, both materials suffer from intrinsic limitations that constrain the final device performance. In order to overcome the limitations of the two materials alone, their combination has been proposed as a solution to the problems. Here we report on the fabrication of an atomic layer deposited (ALD) Fe2O3 coating on porous ALD-TiO2. Our results show that successful implementation requires complete mixing of the TiO2 and Fe2O3 layers via annealing resulting in the formation of a photoactive iron titanium oxide on the surface. Moreover, we found that incomplete mixing leads to crystallization of Fe2O3 to hematite that is detrimental to the photoelectrochemical performance. IPCE and transient photocurrent measurements performed using UV and visible light excitation confirmed that the iron titanium oxide extends the photocurrent generation to the visible range. These measurements were complemented by transient absorption spectroscopy (TAS), which revealed a new band absent in pristine hematite or anatase TiO2 that we assign to charge transfer within the structure. Taken together, these results provide design guidelines to be considered when aiming to combine TiO2 and Fe2O3 for photoelectrochemical applications.
  • Tawfeek, Hendawy N.; Hassan, Alaa A.; Brase, S.; Nieger, M.; Mostafa, Yaser A.; Gomaa, Hesham A. M.; Youssif, Bahaa G. M.; El-Shreef, Essmat M. (2022)
    A series of novel thiazolidine-4-one derivatives was synthesized by reacting 1,4disubstituted hydrazine carbothioamides with diethyl azodicarboxylate. The structures were confirmed by spectroscopic data as well as single-crystal X-ray analyses. The antiproliferative activity of the synthesized compounds was investigated against four human cancer cell lines using an MTT assay. Compounds 5d, 5e, and 5f revealed the most potent antiproliferative activity with GI50 values ranging from 0.70 mM to 1.20 mM, compared to doxorubicin GI50 value = 1.10 mM. Compounds 5d, 5e, and 5f were further investigated for their inhibitory activities against CDK2 and EGFR as potential targets for their molecular mechanism. Compounds 5e and 5f have showed potent inhibitory activity to CDK2 enzyme with IC50 values of 18 and 14 nM, which is more potent than the reference dinaciclib (IC50 = 20 nM). Moreover, compounds 5e and 5f were the most potent EGFR inhibitors, with IC50 values of 93 and 87 nM, respectively, compared to the reference erlotinib (IC50 = 70 nM). In addition, the most potent derivatives were tested for their apoptotic activity against caspases 3, 8, and 9, and the results showed that compounds 5d, 5e, and 5f revealed a greater increase in active caspases 3,8 and 9 than doxorubicin. Also, compounds 5d, 5e, and 5f elevated cytochrome C levels in the MCF-7 human breast cancer cell line by about 15.5, 15.8, and 16.5 times, respectively. Finally, a molecular docking study was performed to investigate the binding sites of these compounds within the active sites of CDK2 and EGFR targets, and the results confirmed that the most potent CDK2 and EGFR inhibitor 5h also have showed the highest docking (c) 2022 The Author(s). Published by Elsevier B.V. on behalf of King Saud University. This is an open access article under the CC BY-NC-ND license (