Małgorzata Hołyńska

European Space Agency, The Netherlands

Citation: Gleirscher, M.; Wolfberger, A.; Schlögl, S.; Hołyńska, M.; Hausberger, A. Accelerated Thermo-Catalytic Degradation of Perfluoropolyether (PFPE) Lubricants for Space Applications. Lubricants 2023, 11, 81. https://doi. Abstract: Perfluoropolyethers (PFPE) are a class of frequently used lubricants in space applications due to their high stab...

Tilted fiber Bragg grating (TFBG) sensors were demonstrated to simultaneously measure the material thermomechanical and refractometric state in which they are embedded. In this work, for the first time, TFBGs are investigated for three-parameter monitoring of space-qualified NuSil® CV16-2500 silicone operating during high-vacuum ultraviolet (UV) ex...

Astronauts are spending longer periods locked up in ships or stations for scientific and exploration spatial missions. The International Space Station (ISS) has been inhabited continuously for more than 20 years and the duration of space stays by crews could lengthen with the objectives of human presence on the moon and Mars. If the environment of...

The sluggish kinetics of oxygen-evolution reaction (OER) through water-oxidation reaction results in high overpotentials for water splitting. Among different compounds, carbon-based material/Mn oxide composites were reported as OER catalysts. Fullerene soot (FS), which contains a mixture of fullerenes and carbon blacks, is low-cost compared to full...

Human presence on Moon and Mars requires oxygen gas production and healthy living conditions. O2 may exist in regoliths of solar bodies as Reactive Oxygen Species (ROS). We propose a device (OxR, Oxygen Release), that indirectly measures ROS (superoxide radical, O2 • , and peroxides, O2 2−) by quantitatively measuring released O2 by their conversio...

A smart composite device for space debris capturing has been manufactured and tested. Shape memory polymer composites (SMPCs) have been used for the production of 4 clamping fingers, consisting of passive carbon fiber reinforced (CFR) laminates joined at their ends by active CFR-SMPC hinges. The shape trigger is provided by heat thanks to the use o...

Water-oxidation reaction (WOR) is a sluggish reaction for hydrogen production through water splitting. Herein, Mn oxide/mesoporous carbon (MC) is introduced as an active WOR catalyst under neutral conditions. The composite was synthesized through the reaction of permanganate and MC using a simple and low-cost procedure and characterized by scanning...

A new mixed-valence Cu I /Cu II three-dimensional coordination polymer, poly[[diaquabis[μ 4 -2-(pyrazin-2-yl)quinoline-4-carboxylato]dicopper(I)copper(II)] bis(tetrafluoridoborate)], {[Cu 3 (C 14 H 8 N 3 O 2 ) 2 (H 2 O) 2 ](BF 4 ) 2 } n , was synthesized and characterized, with 2-(pyrazin-2-yl)quinoline-4-carboxylic acid being employed as a linker...

In this research the ageing of a silicone adhesive in a simulated space environment is monitored through an embedded three parameter tilted Fibre Bragg Grating (TFBG) sensor. Here, the silicone is used as an adhesive between two thin cover glasses, and the space environmental ageing is simulated by thermal cycles in high vacuum conditions (better t...

This research demonstrates the promising abilities of a tilted Fibre Bragg Grating (TFBG) sensor for monitoring the status of a silicone adhesive during a simulated space environment exposure. The silicone is used as adhesive between two thin cover glasses and the TFBG is embedded into the polymer such that it is fully enclosed. Then, the sample is...

The objective of this activity was to develop novel European polyurethane (PU) materials suitable for versatile space applications that can be manufactured via “environmentally friendly” procedure without the use of toxic isocyanates and/or employing sustainable materials sources. The non-isocyanate polyurethanes (NIPUs) were formulated as systems...

This paper summarizes the lessons learnt so far from the application of various advanced techniques for characterising space lubricants:-vapour pressure characterization testing, a method developed to increase the accuracy of evaporation and contamination analysis by measuring the outgassing of contaminants and evaporation of bulk material.-tests f...

Antimicrobial coatings and surfaces for space applications, including organic, inorganic, hybrid coatings, both commercial solutions and solutions under development are reviewed in article number 2100118 by David Duday, Małgorzata Hołyńska, and co‐workers. For applications on confined space stations, the biocompatible coatings must inhibit all kind...

An overview of the current surface treatments/coatings that introduce antimicrobial properties to the exposed surfaces in confined space stations is provided. General aspects, such as biofilm formation and the specific requirements associated with this application, are discussed. Antimicrobial coatings used on the International Space Station (ISS)...

The Bepi Colombo spacecraft was successfully launched on 20th October 2018 and is now on its way to Mercury. The materials and coatings on the Mercury Planetary Orbiter (MPO) and Mercury Transfer Module (MTM) solar arrays will need to withstand a prolonged extreme environment of high-intensity UV radiation at high-temperature (HIHT). The solar arra...

The thermo-oxidative degradation of a multiply-alkylated cyclopentane (MAC) lubricant for space applications is investigated. Accelerated aging tests at temperature levels between 60 °C and 150 °C are performed and the aging behavior is investigated in detail with spectroscopic, mass spectrometric and chromatographic techniques as well as tribologi...

Liquid lubricants and greases used in space applications are generally susceptible to degradation or aging. Depending on the specific material combination and storage conditions, aging effects are also relevant for long-term storage (LTS). An overview on both physical and chemical aging processes for liquid lubricants and greases is given and proce...

New era of human space exploration is about to start: after more than 17 years of successful operations on the International Space Station (ISS), ESA and its international partners are working on a return to the Moon with the now starting construction of an orbital “base camp”, Lunar (Deep Space) Gateway, that will serve to perform robotic and huma...

A series of model dinuclear manganese(IV) complexes of the general formula [(H3COH)(L′)MnIV(μ-L)2MnIV(L′)(HOCH3)] is presented. These compounds feature capping 4,6,10-trihydroxo-3,5,7-trimethyl-1,4,6,10-tetraazaadamantane ligands derived from a polydentate oxime compound (L′). The bridging ligands L include azide (1), methoxide (2), and oxalate (3)...

This review focuses on advanced materials already used and suitable for application in (future) lunar extravehicular activity space suits. A historical and current literature/market survey is presented. Different functional layers of an astronaut garment are defined with emphasis on the external layers subjected to abrasive action of lunar regolith...

Employment of the organic 2-(pyridin-4-yl)quinoline-4-carboxylic acid ligand with extended coordination capabilities leads to the formation of the one-dimensional copper(II) coordination polymer catena -poly[[diaquacopper(II)]-bis[μ-2-(pyridin-4-yl)quinoline-4-carboxylato]-κ ²N² : O ;κ ²O : N ], {[Cu(C 15 H 9 N 2 O 2 ) 2 (H 2 O) 2 ]·2H 2 O} n , und...

This review focuses on advanced materials already used and suitable for application in (future) lunar extravehicular activity space suits. A historical and current literature/market survey is presented. Different functional layers of an astronaut garment are defined with emphasis on the external layers subjected to abrasive action of lunar regolith...

Even 155 years after their first synthesis, Schiff bases continue to surprise inorganic chemists. Schiff-base ligands have played a major role in the development of modern coordination chemistry because of their relevance to a number of interdisciplinary research fields. The chemistry, properties and applications of transition metal and lanthanoid...

Cyanobacteria, green algae, and higher plants provide the major part of molecular O2 of Earth atmosphere via water oxidation of oxygenic photosynthesis. The water-oxidizing complex is a manganese-calcium oxide-based cluster embedded in Photosystem II that oxidizes water with high turnover frequency. The atomic structure and analysis of the Mn-Ca cl...

The blue-green, mononuclear copper complex [CuL(NO3)]NO3, (1), was synthesized by reacting copper nitrate with L = tris(2-hydroxyliminopropyl)amine in methanol. The structure of 1 was determined by single-crystal X-ray diffraction, which revealed a copper(II) ion that exhibits a pseudo-octahedral coordination geometry. While one of the nitrate anio...

BepiColombo is a mission planned by the European Space Agency (ESA) to reach Mercury, the least explored planet in our Solar System. The mission has been launched on October 20, 2018, and will face long-term exposure to temperatures up to 400°C, thermal cycling between extreme temperature values, and high levels of radiation (UV, protons). A new th...

Herein the role of a mononuclear cobalt(III) complex, [CoIII(DPKOH)2]ClO4 (DPK = di(2-pyridyl) ketone) in the water electrooxidation process is investigated with scanning electron microscopy, energy dispersive spectrometry, X-ray diffraction studies, NMR, chronoamperometry, cyclic voltammetry, extended X-ray absorption fine structure and X-ray abso...

This chapter begins with a definition of a single‐molecule magnet (SMM). Molecular architecture is the key to understanding the magnetic properties of SMMs; therefore, X‐ray diffraction studies have played a crucial role in the characterization of SMMs and require optimization of their synthesis/crystallization conditions. There are other magnetica...

3D printing will revolutionize the manufacturing industry. Significant advances in computer aided design, additive manufacturing and materials science have opened up the possibilities of self-assembly systems, self-healing and material property alterations. Printing layer by layer allows complex geometries to be built, previously difficult under co...

Correction for ‘Water oxidation by a copper( ii ) complex: new findings, questions, challenges and a new hypothesis’ by Mohammad Mahdi Najafpour et al. , Dalton Trans. , 2018, 47 , 9021–9029.

Four new manganese(IV) complexes with cyclic form of the tripodal oxime ligand tris(2-hydroxyiminopropyl)amine (Ox3H3 L1) and bis(benzimidazole) (Bbim) auxiliary ligand were prepared and characterized in terms of their crystal structures [(L1′Mn (Bbim)CH3OH)3MnO] (1), [L1′Mn(Bbim)H2O]·2CH3OH (2), ([L1′Mn(Bbim)CH3OH]·CH3OH ∙ 1/2 Bbim (3) and [(L1′Mn...

Copper(II) complexes are very promising catalysts for water oxidation. Herein new findings for the water-oxidizing activity of a few copper(II) complexes under the water oxidation conditions are reported. Copper compounds in this study are copper(II) phthalocyanine-3,4′,4″,4″′-tetrasulfonic acid tetrasodium salt (1), the product from the hydrolysis...

Herein we report on a poly-peptide/Mn oxide nanocomposite as a model for water-oxidizing catalyst in Photosystem II. The material is obtained by the reaction of poly-L-tyrosine, Mn(OAc)2•4H2O and KMnO4. HRTEM images of the nanocomposite indicate the presence of nanoparticles dispersed in a poly-L-tyrosine matrix with no crystalline phases. A broad...

Four new Pd(II) complexes are presented, [Pd(L1)(Cl)]K (1), [Pd(L1)(Cl)]Na (2), [Pd(L2)(Cl)]Na (3) and [Pd(L2)(H2O)] (4), where the ligands are derived from ortho-vanillin and either L-glutamic acid (L1) or L-tyrosine (L2). The complexes were characterized by X-ray diffraction studies, ESI-MS, IR and NMR spectroscopy and elemental analysis. Complex...

An overview of coatings and thin films for spacecraft applications is provided, focusing on coatings for thermal control and optical applications. An outline of the requirements imposed by the harsh conditions in space is given. Space applications of coatings are listed and their qualification is described, including testing in the ESA laboratories...

A new ligand 2,3′-bipyridine-2′,3-dicarboxylic acid monohydrate (1) and a new copper(II) 2D coordination polymer [Cu(2,3′-2′,3-bpdc)H2O]n(2) (2,3′-2′,3-bpdc = deprotonated bipyridinedicarboxylic acid) were synthesized and characterized by X-ray diffraction studies, IR spectra, elemental analysis, EPR, luminescence spectra and TGA. Magnetic properti...

For the first time, using scanning electron microscopy, transmission electron microscopy, X-ray absorption near edge structure and extended X-ray absorption fine structure X-ray diffraction, it is showed that MnCO3, MnWO4, Mn3(PO4)2•3H2O, MnS and Mn(VO3)2•xH2O under the water-oxidation condition and in the presence of cerium(IV) ammonium nitrate, a...

Herein we report a new strategy to disperse Mn oxide into the apoenzyme of photosystem II. The compound was characterized by scanning electron microscopy, transmission electron microscopy, UV-visible spectroscopy, Fourier transform infrared spectroscopy, X-ray absorption near edge structure, extended X-ray absorption fine structure, X-ray diffracti...

A series of new Fe(III) complexes, [Fe(OVGln)2]Na (1), [Fe(OVGln)2]K (2), [Fe(OVGlu)2]Na (3) and [Fe(OVGlu)2]K (4), with Schiff base ligand derived from ortho-vanillin (OV) and L-glutamine (Gln) or L-glutamic acid (Glu), are presented. The complexes are extensively characterized with mass spectrometry, IR spectroscopy, X-ray powder diffraction, EPR...

Via an oxidation reaction of Cu(I) iodide with pyridine-2,6-dicarboxylic acid (H2L) in DMF, threecopper(II) complexes, [(CH3)2NH2]2[CuL2] (1), K2[CuL2]∙H2L∙H2O (2) and [Cu(L)(H2O)]n (3), were synthesized and characterized. The structures of 1-3 were determined by single crystal X-ray diffraction. In-situ DMF decomposition produces dimethylamine bas...

The condensation reaction of ortho-vanillin and l-cysteine leads to formation of a racemic mixture of (2RS,4R)-2-(2-hydroxy-3-methoxyphenyl)thiazolidine-4-carboxylic acid and not, as reported in the available literature, to a Schiff base. The racemic mixture was fully characterized by 1D and 2D NMR techniques, ESI-MS and X-ray diffraction. Addition...

Herein, holmium oxide as a support for nanosized Mn oxide was used toward the synthesis of a new catalyst for water oxidation. A composite of Mn and Ho oxide was synthesized by a simple hydrothermal procedure and characterized by scanning electron microscopy, extended edge X-ray absorption fine structure, transmission electron microscopy, powder X-...

Tetraethylammonium salt of a new Keggin-type 12-molybdovanadate nanocluster, [(C2H5)4N]4[VMo12O40] (1) was synthesized via reaction between sodium tungstate, ammonium vanadate and tetraethylammonium bromide in acidic medium. Compound 1 was characterized by X-ray crystallography, FT-IR, UV–Vis and cyclic voltammetry and then applied as an efficient...

Nanolayered Mn oxides are among important Mn-based catalysts for water oxidation. Mn(II), (III) and (IV) ions are present in the structure, and thus, electrochemistry of the solid is very complicated. Herein, the cyclic voltammetries of the nanolayered Mn oxides in the presence of LiClO4 at pH= 6.3, under different conditions, were studied using sc...

Structure and properties of the rare metal complex of the chiral Schiff base ligand derived from ortho-vanillin and L-tyrosine are presented. This study is a continuation of research on ligands containing biologically compatible moieties. The ligand is also fully characterized in form of a sodium salt, in particular in solution, for the first time....

Synthesis and properties of a new rigid tripodal oxime ligand are reported. The ligand is a derivative of phloroglucine with three carboxime arms alternate with hydroxyl groups and three intramolecular O[sbnd]H⋯N hydrogen bonds. Intermolecular O[sbnd]H⋯O hydrogen bonds result in formation of a characteristic three-dimensional network. The structure...

Herein we report on the synthesis and characterization of nano-sized Mn oxide/silica aerogel with low density as a good catalyst toward water oxidation. The composite was synthesized by a simple and low-cost hydrothermal procedure. In the next step, we studied the composite in the presence of cerium(IV) ammonium nitrate and photo-produced Ru(bpy) 3...

Herein, we report on nano-sized Mn oxide/carboxylic acid or amine-functionalized carbon nanotubes as water-oxidizing composites in artificial photosynthesis. The composites are synthesized by simple procedures and characterized by different methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV)...

Herein, we report on nano-sized Mn oxide/carboxylic acid or amine-functionalized carbon nanotubes as water-oxidizing composites in artificial photosynthesis. The composites are synthesized by simple procedures and characterized by different methods. The water-oxidizing activities of these composites are also considered in the presence of cerium(IV)...

Plants, algae and cyanobacteria capture sunlight, extracting electrons from H2O to reduce CO2 into sugars, while releasing O2 in the oxygenic photosynthetic phenomenon. Because of the important role of water oxidation for artificial photosynthesis and many solar fuel systems, understanding the structure and function of this unique biological cataly...

Water splitting to produce H2 is an important procedure for the conversion of intermittent energies. However, the reaction is energetically limited by the water-oxidation process. Herein, we report the synthesis of Mn oxide on nanoparticles of KAl3(SO4)2(OH)6, Co3O4, CuO, Fe3O4, MgO, NiO, SiO2, SnO2, TiO2, WO3, zeolite, ZnO and ZrO2 by a simple, lo...

The solar energy is intermittent, and thus, to be practical at a huge scale, will require a large capability for energy storage. One approach involves artificial photosynthesis to drive solar energy for water splitting into hydrogen or to reduce CO2 to reduced carbon fuels. In such reactions, cheap electrons from water oxidation are critical. Herei...

The reaction of an Eu(III) complex of the protonated form of the macrocyclic Schiff base derived from 1,3-diamino-2-hydroxypropane and 2,6-diformylphenol, [Eu(H4L)Cl3], with three equivalents of base results in a mononuclear complex of the triply deprotonated form of the ligand, [Eu(HL)]. The photophysical properties of the [Eu(HL)] complex are dis...

Studies of the stability of a ligand derived from L-glutamic acid and ortho-vanillin and its new [Cu4] complex are presented. The [Cu4] complex contains a heterocubane [CuII4O4] core and pendant carboxylic groups increasing its solubility in water, also under basic conditions. The stability of the complex in different solvents is confirmed with ESI...

Three highly porous Zr(iv)-based metal-organic frameworks, UBMOF-8, UBMOF-9, and UBMOF-31, were synthesized by using 2,2'-diamino-4,4'-stilbenedicarboxylic acid, 4,4'-stilbenedicarboxylic acid, and combination of both linkers, respectively. The mixed-linker UBMOF-31 showed excellent hydrogen uptake of 4.9 wt% and high selectivity for adsorption of...

Currently, the leading approach for extraction of uranium from seawater is selective sorption of UO2 2+ ions onto a poly(acrylamidoxime) fiber. Amidoxime functional groups are the most studied extractant moieties for this application, but are not perfectly selective, and understanding how these groups (and more generally the oxime groups) interact...

Two metal-organic frameworks (MOFs) with pyridine-3,5-dicarboxylic acid (H2pdc), {[CuII][CuII(pdc)(H2O)]⋅1.5MeCN⋅H2O}n (1) and {[Cu(MeCN)4]⋅2[CuII]⋅2[CuII2(pdc)2(H2O)1.5(OH)0.5]⋅⋅ ⋅MeCN⋅4AcOH⋅8H2O}n, (2) (MeCN = acetonitrile, AcOH = acetic acid) containing both [CuxIx] (x = 4 for 1 and x = 2 for 2) and Cu2(COO)4 clusters at the same time were synth...

Herein the effect of support on water-oxidizing activity of amorphous Mn oxides was investigated. We used nanoparticles of CuO, NiO, MgO, SiO2 or ZrO2 as support and placed Mn oxides on these oxides. The compounds were synthesized by a simple procedure and characterized by high-resolution transmission electron microscopy, X-ray photoelectron spectr...

The reaction of KMnO4 with cobalt nanoparticles coated with SiO2 layers forms a highly dispersible, magnetically separable and environmentally friendly catalyst toward water oxidation. The compound was characterized by scanning electron microscopy, energy-dispersive spectroscopy, transmission electron microscopy, X-ray Photoelectron Spectroscopy, X...

A tetranuclear copper (II) complex with pyrazole-3,5-dicarboxylate ligands (pdc3−), [Me2NH2]4[Cu4(pdc)4], was synthesized using solvothermal and metal oxidation routes and characterized by elemental analysis, infrared, thermogravimetry/differential thermal analysis, and room-temperature magnetic measurements. The structure of the complex was determ...

All cyanobacteria, algae, and plants use a similar water-oxidizing catalyst for water oxidation. This catalyst is housed in Photosystem II, a membrane-protein complex that functions as a light-driven water oxidase in oxygenic photosynthesis. Water oxidation is also an important reaction in artificial photosynthesis because it has the potential to p...

Using sustainable energies, large-scale electrochemical and photochemical hydrogen production from water splitting are greatly limited by water-oxidation reaction. Herein we report that nanolayered Mn oxide obtained in the reaction of KMnO4 and Mn2CO10 is a good catalyst toward water oxidation. The Mn oxide was synthesized by a simple method and ch...

Correction for ‘Gold nanorods or nanoparticles deposited on layered manganese oxide: new findings’ by Mohammad Mahdi Najafpour et al., New J. Chem., 2015, 39, 7260–7267.

The water-oxidizing complex or oxygen-evolving complex in plants, algae and cyanobacteria is a Mn4CaO5 cluster catalyzing light-induced water oxidation. Herein we report that nano-sized Mn oxide/carbon aerogel is an active and low-density catalyst toward water oxidation. The composite was synthesized by a simple, low-cost procedure with different r...

The new 2D coordination polymer with a new 3,3'-bipyridine-2,2'-dicarboxylate monohydrate (3,3'-bpdc center dot H2O) ligand is described: [Mn(3,3'-bpdc)](n). In the distorted octahedral coordination environment of the Mn2+ cations the 3,3'-bptc ligand is bonded through nitrogen/carboxylate oxygen atoms. The [Mn(3,3'-bpdc)](n) polymer is characteriz...

The synthesis, structure, and magnetic properties of five lanthanide complexes with multidentate oxime ligands are described. Complexes 1 and 2 (1: [La2 (pop)2 (acac)4 (CH3 OH)], 2: [Dy2 (pop)(acac)5 ]) are synthesized from the 2-hydroxyimino-N-[1-(2-pyridyl)ethylidene]propanohydrazone (Hpop) ligand, while 3, 4, and 5 (3: [Dy2 (naphthsaoH)2 (acac)4...

Herein we consider the role of platinum nanoparticles on water-oxidation catalyzed by manganese oxide. The nanocomposites were synthesized by two different methods and characterized by scanning electron microscopy, energy dispersive spectrometry, high resolution transmission electron microscopy, X-ray diffraction, Fourier transform infrared spectro...

The (NH4)12[Mo36(NO)4O108(H2O)16]·30.84H2O ({Mo36}) catalyst has been synthesized and successfully employed in the selective oxidation of various sulfides to sulfoxides with urea hydrogen peroxide as oxidant under mild reaction conditions with 84–99 % conversion and 58–99 % selectivity, with active functional groups such as the hydroxy group and C=...

Herein we consider the role of gold nanorods, with diameter ~10 nm or nanoparticles (size <100 nm), deposited on nanolayered Mn oxide toward water oxidation. The catalysts were synthesized by simple methods and characterized by scanning electron microscopy, energy dispersive spectrometry, high resolution transmission electron microscopy, X-ray diff...

We synthesized manganese oxides supported on gold nanoparticles (diameter <100 nm) by the reaction of KMnO4 with gold nanoparticles under hydrothermal conditions. In this green method Mn oxide is deposited on the gold nanoparticles. The compounds were characterized by scanning electron microscopy, energy-dispersive spectrometry, high resolution tra...

A series of new oxime-bridged copper(II) complexes is introduced with phenyl 2-pyridyl ketoxime (ppkoH) as a ligand: polymeric [Cu-2(ppko)(2)(ppkoH)(2)](NO3)(BF4)center dot CH3OH (1), dinuclear [Cu-2(ppko)(2)(ppkoH)(2)](ClO4)(2) (2), [Cu-2(ppko)(2)(ppkoH)](ClO4)(2)center dot 0.75CH(3)OH (3), trinuclear [Cu-3(OH)(ppko)(3)(CH3OH)]center dot[Cu-3(OH)(...

Abstract 2,2′-Bipyridine-4-methyl-3,3′-dicarboxylic acid monohydrate (1) is introduced as a new organic ligand. Synthesis, structure and properties (TGA, IR, NMR) are characterized. 1 includes an extensive hydrogen bonding network with formation of various graph-set motifs, such as \( {\text{R}}_{2}^{2} \left( { 1 8} \right) \) or \( {\text{R}}_{12...

Manganese oxide structure with lanthanum(III) or cerium(III) ions between the layers was synthesized by a simple method. The ratio of Mn to Ce or La in samples was: 0.00, 0.04, 0.08, 0.16, 0.32, 0.5, 0.82 or 1.62. The compounds were characterized by scanning electron microscopy, transmission electron microscopy, X-ray diffraction studies, and atomi...