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1

Technological aspects of synthesis of poly(ethylene glycol) mono-1-propenyl ether monomers

Urbala Magdalena

Polish Journal of Chemical Technology

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2020

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Vol. 22, nr 3

55--63

EN

For the first time, the technological aspects of the highly productive and selective synthesis of UV-reactive poly(ethylene glycol) mono-1-propenyl ether monomers was developed. The solvent-free isomerization of model commercial available 2-allyloxyethanol and allyloxypoly(ethylene glycol) derivatives, type Allyl–[OCH2CH2]n–OH, n = 1–5, into a 1-propenyl derivative under the homogeneous catalysis conditions using the ruthenium complexes were evaluated. The effect of a various reaction conditions (i.e. the concentration of [Ru] complex, the reaction temperature, reaction gas atmosphere) together with trace amounts of allyl hydroperoxides formed via autoxidation reaction of allyl substrates on the productivity of catalyst was examined in detail. Moreover, the significant role of the allyl substrate structures on the catalytic activity of ruthenium catalysts were also recognized. The optimal parameters of the scaled-up synthesis together with productivity of catalyst were first established.

2

Montmorillonite as the catalyst in oxidation of limonene with hydrogen peroxide and in isomerization of limonene

Malko M., Antosik A. K., Wróblewska A., Czech Z., Wilpiszewska K., Miądlicki P., Michalkiewicz B.

Polish Journal of Chemical Technology

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2017

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Vol. 19, nr 4

50--58

EN

In our studies montmorillonite (MMT) was used as the heterogeneous, natural catalyst. This material was previously prepared by bentonite purification with help of the sedimentation method. The obtained catalyst was characterized by: XRD, SEM, BET and EDX. Catalytic tests with montmorillonite as the catalyst were performed with the natural terpene – R-(+)-limonene. This compound was oxidized with hydrogen peroxide and, moreover, in the separate process it was also isomerized. As the main products of limonene oxidation were detected: (1,2-8,9)-diepoxide, perillyl alcohol, carvone, carveol, 1,2-epoxylimonene and 1,2-epoxylimonene diol. In the isomerization of R-(+)-limonene were formed: terpinenes, terpinolene and p-cymene. Conversions of limonene in these processes reached 70–80%. The application of montmorillonite (the natural of origin) in the studied processes (oxidation and isomerization) is environmentally friendly, it allows to reduce the cost of the studied processes. The resulting products of the processes of oxidation and isomerization of R-(+)-limonene have many applications.

3

Znaczenie R-(+)-limonenu, jako surowca do syntez w chemii organicznej i dla przemysłu organicznego

Malko M. W., Wróblewska A.

Chemik

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2016

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Vol. 70, nr 4

193--202

PL

Stosowane obecnie, nowoczesne technologie produkcji związków chemicznych wykorzystują surowce odnawialne do produkcji kluczowych produktów dla różnych gałęzi Przemysłu, m.in. dla przemysłu kosmetycznego, czy spożywczego. Takim surowcem odnawialnym jest na przykład limonen. R(+)-limonen znalazł zastosowania w przemyśle kosmetycznym, perfumeryjnym, spożywczym, w aromatoterapii, w syntezach chemicznych jako reagent, a także jako rozpuszczalnik oraz w produkcji polimerów. Związek ten występuje w skórkach owoców cytrusowych, które stanowią produkt uboczny z przemysłu produkującego soki i może być z nich pozyskiwany metodą destylacji prostej lub metodą destylacji z parą wodną. Szereg związków o właściwościach zapachowych, lub wykazujących działanie biologicznie aktywne (mających zastosowanie w medycynie), ma zbliżony do R-(+)-limonenu szkielet węglowy, co powoduje, że związek ten znalazł zastosowanie do ich otrzymywania, często na drodze prostych, jedno- lub dwuetapowych przemian. Do związków tych należą: α-terpineol, karweol, karwon, alkohol perillowy, mentol i 1,2-tlenek limonenu (utlenione pochodne limonenu) oraz powstający na drodze odwodornienia limonenu p-cymen. Wszystkie te związki są o wiele cenniejsze niż limonen i mają zastosowanie w przemyśle perfumeryjnym i spożywczym, jako składniki kompozycji zapachowych do aromatyzowania kosmetyków, napojów i żywności.

EN

The modern technologies which are currently applied in the production of organic compounds are using renewable raw materials for the obtaining of key products for the various branches of industry, including cosmetics or food industry. R-(+)-limonene is a such renewable raw material. R-(+)-limonene has found applications not only in the cosmetic, perfume and food industry, but also in aromatherapy, and in chemical syntheses as a reagent, as a solvent and in the production of polymers. This compound is present in the peels of citrus fruits, which are the waste product from the citrus juice industry. R-(+)-limonene can be obtained from orange peels by a simple distillation or by a steam distillation. A lot of olfactory compounds or biologically active compounds (which are applied in medicine) have the structure similar to R-(+)-limonene structure. It causes that this compound can be applied in their synthesis, very often in very simple one-or two-step reactions. These compounds include: α-terpineol, carvone, carveol, perillyl alcohol, menthol and 1,2-epoxylimonene (the oxidized derivatives of limonene) and formed by the dehydrogenation of limonene – p-cymene. All of these compounds are much more valuable than limonene and are used in perfume and food industry, and also as components of olfactory compositions for flavoring cosmetics, beverages and food.

4

Metody wytwarzania izo-α-kwasów

Dobrzyńska-Inger A., Rój E., Kostrzewa D.

Przemysł Chemiczny

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2014

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T. 93, nr 8

1321-1327

PL

Omówiono rolę chmielu i ekstraktu chmielowego jako głównej przyprawy podczas wytwarzania piwa. Wyjaśniono podstawową reakcję, której ulegają chmielowe α-kwasy w brzeczce warzelnej oraz wpływ tej reakcji na smak piwa. Przedstawiono metody wytwarzania pochodnych α-kwasów poza kotłem warzelnym.

EN

A review, with 50 refs., of chem., thermal and photochem. methods for isomerization of α-acids in hop exts.

5

Hiperwalentne związki siarki, selenu i telluru. Część 4. Selenurany i tellurany

Zając A.

Wiadomości Chemiczne

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2012

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[Z] 66, 11-12

1119-1144

EN

In this part selenuranes (10-Se-4 and 10-Se-5) and perselenuranes 12-Se-6 as well as telluranes 10-Te-4 and pertelluranes 12-Te-6 will be presented. The main goal is to describe recent reports on the synthesis, chemical, physical, spectral and conformational behavior, stereochemistry, stability and biological activity of these compounds. Their occurrence as reaction intermediates will also be shown.

6

Hiperwalentne związki siarki , selenu i telluru. Część 3. Sulfuran Martina , sulfurany 10-S-5 i 12-S-6

Zając A.

Wiadomości Chemiczne

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2012

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[Z] 66, 9-10

893-907

EN

In this part of the review one of the most famous 10-S-4 sulfurane called Martin sulfurane together with sulfuranes 10-S-5 and persulfuranes 12-S-6 will be presented. Martin sulfurane has been well known for a relatively long time but it is still useful in organic synthesis as a dehydrating, coupling and oxidizing agent. Its use in selected substitution reactions will be also described. Next, synthesis and selected properties of sulfuranes 10-S-5, mainly sulfurane oxides, and persulfuranes 12-S-6, will be shown. Besides synthetic methods, the review is focused on the investigations of the stability and isomerization of these types of compounds, which is particularly interesting for persulfuranes, because of the presence of three 3c-4e bonds.

7

Hiperwalentne związki siarki, selenu i telluru. Część 2. Sulfurany 10-S-3 i 10-S-4

Zając A.

Wiadomości Chemiczne

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2012

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[Z] 66, 7-8

593-622

EN

The compounds presented herein are sulfuranes 10-S-3 and 10-S-4 containing hypervalent sulfur atom. They have been known for a relatively long time. Nevertheless, they, and especially 10-S-4 species, are still of great interest due to their unique properties. The review presents recent approaches to the synthesis of these compounds, their selected structural, physical, chemical, stereochemical and electronic properties and their use as reagents and catalysts in several reaction types. The presence of structures of these types as intermediates, which explains selected reaction mechanisms, will also be shown.

8

Hiperwalentne związki siarki, selenu i telluru. Część 1. Charakterystyka ogólna

Zając A.

Wiadomości Chemiczne

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2012

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[Z] 66, 5-6

529-541

EN

The goal of this four-part review is a presentation of the results of recent studies on the properties and chemistry of hypervalent sulfur, selenium and tellurium compounds. The term “hypervalency” has been known since 1969 when Musher used it to describe molecules bearing heteroatoms which formally did not fulfill the octet rule. This violation was explained by the postulate concerning the existence of a 3-center 4-electron bond between a hypervalent heteroatom and two axial electronegative ligands. The bond is the a combination of two ligand orbitals and a pz orbital of a central heteroatom which results in the formation of three molecular orbitals. The distances between the central atom and these two ligands are longer than the length of the typical sp2 bonds, such as equatorial ones. Moreover, the effective electron density is shifted from the central atom towards the axial ligands what results in the fulfillment of the octet rule of this atom. The geometry of this system is trigonal bipyramid (Fig. 2), except from compounds having three 3-center 4-electron (3c-4e) bonds which have tetragonal bipyramid geometry (Fig. 3). The term “geometry” includes positions of ligands and lone electron pairs. The stability of hypervalent compounds is affected by a few factors: electronegativity of ligands, formation of five-membered cyclic structures involving the central atom and the number of electron shells of the central atom. Martin proposed three-symbol notation N-X-L for these structures, which was further modified (Tab. 1). Hypervalent compounds can isomerize according to various mechanisms: Berry pseudorotation (Scheme 1), turnstile rotation (Scheme 2), cuneal inversion (Scheme 3), lever mechanism (Scheme 4), or Bailar twist (Scheme 5). Furthermore, hypervalent structures of 10-X-4 and 10-X-5 type with trigonal bipyramid geometry, C1 or C2 symmetry and at least three different ligands can exist as optically active species (Tab. 2, Fig. 5–7, Scheme 6), especially the "spiro" ones, which are resistant to isomerization. In 1977 Martin and Balthazor proposed extended Cahn-Ingold-Prelog convention for description of the absolute configuration of chiral hypervalent compounds (Fig. 5).

9

Intensyfikacja wykorzystania ekstraktu chmielowego do produkcji piwa

Skorek U., Hubicki Z., Rój E.

Chemik

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2011

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Vol. 65, nr 3

160-163

PL

Dokonano przeglądu metod intensyfikacji wykorzystania ekstraktów chmielowych poprzez ich izomeryzację. Omówiono dostępne izomery w obrocie handlowym wraz z ich charakterystyką. Przedstawiono Nowe Międzynarodowe Normy do analizy ilościowej zizomeryzowanych a-kwasów metodą chromatografii HPLC .

10

Możliwości zagospodarowania odpadów chloroorganicznych

Myszkowski J., Milchert E., Paździoch W., Bartkowiak M., Pełech R.

Wiadomości Chemiczne

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2010

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[Z] 64, 5-6

493-506

EN

Possible ways of utilization of waste chloroorganic compounds have been presented. The methods like isomerization, hydrodechlorination, ammonolysis and chlorolysis have been described. Practical application of these methods allows the management of chloroorganic wastes coming from waste water and waste streams formed e.g. in the production of vinyl chloride by dichloroethane method [2] and in the production of propylene oxide by chlorohydrin method [1]. Four valuable methods of chlorocompounds utilization have been discussed. The first one is isomerization of 1,1,2-trichloroethane [3, 4] to 1,1,1-trichloroethane as the valuable product with a less toxicity than the substrate. The second method is ammonolysis of waste 1,2-dichloropropane and 1,2,3-trichloropropane. Third described method is hydrodechlorination [5, 6] of chloroorganic compounds, especially used for reduction of chlorophenols, vinyl chloride and 1,2-dichloroethan. The last discussed method is the chlorolysis [1, 7]. This method can be used for utilization of all types of waste chloroorganics. Separation of waste chloroorganic compounds by adsorption methods [8–11] has also been described in the article.

11

Utilization of waste chloroorganic compounds

Myszkowski J., Milchert E., Bartkowiak M., Pełech R.

Polish Journal of Chemical Technology

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2010

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Vol. 12, nr 3

36-39

EN

Efficient methods of utilization of waste chloroorganic compounds coming from waste water and the waste streams formed e.g. in the production of vinyl chloride by dichloroethane method and in the production of propylene oxide by chlorohydrin method have been presented. First the separation of chloroorganic wastes by the adsorption methods has been described in the article. Three valuable methods of hlorocompounds utilization have been then discussed. The first one is isomerization of 1,1,2-trichloroethane to 1,1,1- trichloroethane as the valuable product with less toxicity than a substrate. The second method is ammonolysis of waste 1,2-dichloropropane and 1,2,3-trichloropropane. The third described method is chlorolysis. This method can be used for the utilization of all types of waste chloroorganics.

12

Wybrane aspekty zastosowania reakcji izomeryzacji w technologii bisfenolu A

Kulesza K., Tkacz B., German K., Bartoszewicz P.

Przemysł Chemiczny

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2009

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T. 88, nr 6

678-681

13

Structural Studies of Position 2 Modified Endomorphin-2 Analogs by NMR Spectroscopy and Molecular Modeling

Janecka A., Perlikowska R., Gach K., Fichna J., Mazur A., Kruszyński R., Janecki T., Jankowski S.

Polish Journal of Chemistry

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2009

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Vol. 83, nr 7

1293-1307

EN

Endomorphin-2 (EM-2, Tyr-Pro-Phe-Phe-NH2) is an endogenous ligand for the mi-opioid receptor. To examine the importance of Pro2 in EM-2 structure, we synthesized a series of analogs in corporating piperidine-2-, 3- and 4-carboxylic acids (Pip, Nip and Inp, respectively) in position 2. Pip, Nip and Inp are six-membered mimics of Pro and can be considered as alfa-, beta- and gamma-amino acids, respectively. Receptor binding studies revealed that [(R)-Nip2]EM-2 had greatly in creased mi-opioid receptor affinity compared with the parent peptide, while two other analogs were in active. In order to determine which structural elements of [(R)-Nip2]EM-2 could be responsible for the out standing affinity of this analog, the solution conformations of EM-2 analogs in corporating Promimics were investigated by the combination of 2D 1H NMR measurements and molecular modeling calculations. Evaluating the ratios of cis/trans rotamers, aromatic inter actions and dihedral angles we have found that all three analogs exist as a mixture of cis/trans rotamers of the Tyr–Xaa peptide bond and have flexible, extended conformations, with no intramolecular hydrogen bonds or aromatic ring inter actions observed for EM-2. The obtained results do not allow to draw conclusions on the bioactive conformation of the most active analog. We can suggest that a well known preference of the substituents to occupy equatorial positions in six-membered rings, to gether with a greater distance between Tyr1 and Phe3 aromatic rings, in Nip, which is a beta-amino acid, as compared with EM-2, are the main differentiating factors which are responsible for the exceptional affinity of [(R)-Nip2]EM-2.

14

Non-linear optical properties of epoxy-based polymers with covalently attache chromophores and metallic complexes

Borshch A., Brodyn M., Lyakhovetsky V., Kutsenko A., Maloletov S.

Materials Science

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2002

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Vol. 20, No. 4

29-48

EN

Non-linearl refraction and absorption in polymer structures based upon diglicidylether of bisphenol A has been studied. The polymers contain organo-metallic complex of nickel(II) NiL(ClO4) 2- or 4-amino-azobenzene as non-linear optically active side groups covalently attached at each monomer unit. The studies have been carried out by polarization technique together with a real time pump and probe technique, dynamic holography and Z-scan. The materials were shown to exhibit fast non-linear response (relaxation time is about 20 ns) together with slow one (relaxation time of the order of tens of hours). This makes it possible to record fast- and long-lived (quasi-stationary) phase holograms. The analysis of possible mechanisms for the polymer refractive index non-linear response in the time range from 10-8 to 105 is presented. In particular, the role of electron polarizability, thermal excitation of the polymer, orientation of the chromophore molecules, and trans-cis isomerization processes are discussed.

15

Badanie węgla zawartego w warstwach malarskich metodą spektroskopii ramanowskiej

Szroeder P., Rozpłoch F., Marciniak W., Rogóż J., Flik J., Rogal R.

Karbo

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2002

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Nr 9

262-264

PL

Celem pracy było zbadanie możliwości zastosowania spektroskopii ramanowskiej do datowania dzieł sztuki. Przedmiotem badań był olej lniany, który jest powszechnie używany jako spoiwo farb olejnych. Zarejestrowano widma ramanowskie próbek olejów obejmujących ostatnie 20 lat. Efekt starzenia zinterpretowano jako skutek izomeryzacji i polimeryzacji. Zidentyfikowano pasma odpowiadające drganiom grup funkcyjnych C=O, O-C oraz O-H. Natężenie linii przypisywanej drganiom szkieletowym niesprzężonych wiązań w łańcuchach węglowodorowych w konformacji cis spada pod upływem czasu. Efekt ten jest wynikiem przejść konformacyjnych (cis-trans) i wysycania podwójnych wiązań węglowych. Widma starszych próbek wykazują silniejszą fluorescencję.

EN

The present study was undertaken to investigate the possibility of use of Raman spectroscopy for dating of artistic paintings. Linseed oil used commonly as binder of oil colors was examined. Raman spectra were recorded for new and aged (till 20 years) oils. The aging effects on the spectra of oils are interpreted as a result of both the positional and conformal isomerization and the polymerization. There were identified bands corresponding to oscillation modes of functional groups C=O, O-C and O-H. The intensity of the line attributed to backbone oscillations of no conjugated hydrocarbon double bonds in cw-conformation shows the time decrease. This effect results from the conformal transitions (cis-trans) and saturation of carbon double bonds. The spectra recorded from the older oils shows a more intensive fluorescence.

16

Physical image vs. structure relation, 5 [1]. Multinuclear NMR structural study on some hydrazones of O,O-Dialkyl 1-Oxoalkanephosphonates

Nazarski R. B., Gralak D. K., Kudzin Z. H.

Bulletin of the Polish Academy of Sciences. Chemistry

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2000

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Vol. 48, No. 1

27-33

EN

An unambiguous method for determination of the configuration of any single 0,0-dialkyl 1-oxoalkanephosphonate hydrazones based on H, C, P NMR data has been elaborated; the use of 1 JCp (P-C=N) couplings is the most fruitful. The 12C/13C isotope effects on the P chemical shifts of selected compounds have been measured. For primary hydrazones the E/Z isomerisation with stabilisation of their Z forms through an intramolecular H-bonding has been proven. In addition, for the latter stereoisomers small scalar couplings between H-bonded groups N-H.. .O=P have been found, JHP 2.4-3.4 Hz. The possibility of the across H-bridge transfer of spin-spin interactions in these forms is also discussed.

17

Selective synthesis of 1,3-di- and 1,3,5-trisubstituted tetrazolium salts by tert-butylation of tetrazole, 1- and 5-monosubstituted tetrazoles, isomerization of 1,3-disubstituted salts to 1,4-salts

Gaponik P.N., Voitekhovich S.V., Maruda I.I., Kulak A.A., Ivashkevich O.A.

Polish Journal of Chemistry

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1998

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Vol. 72, nr 10

2247-2253

EN

Tetrazole and its 1- and 5-monosubstituted derivatives are found to react with tert-butyl alcohol in 72% perchloric acid media, yielding selectively 1,3-di- and 1,3,5-trisubstituted tetrazolium salts. 1,3-Disubstituted salts are slowly converted under the same conditions into the corresponding 1,4-disubstituted salts. This transformation may be used for selective synthesis of the latter.

18

N-pentane isomerization in the presence of BCl3 containing superacids

Marczewski M., Dębowiak M., Przerwa K.

Polish Journal of Chemistry

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1998

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Vol. 72, nr 9

2115-2126

EN

New superacid catalysts have been obtained by the action of BCl3 vapours on silicaalumina (87% SiO2). The mechanism and kinetics of pentane isomrerization is discussed.

19

Isomerization of vegetable oils catalyzed by ruthenium complexes

Krompiec S., Suwiński J., Majewski J., Grobelny J.

Polish Journal of Applied Chemistry

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1998

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Vol. 42, nr 1

43-48

EN

A study on isomerization of industrial oils - rapeseed, soybean, suntlower and linseed - was performed in the presence of the following ruthenium complexes: [RuHCl (CO)(PPh(3), [Ru(CO)3(PPh(3)2], [Ru(C2(1,5-COD)]x [Ru(acac)3], [RuCl2(PPh3)3)3], (RuH2(PPh3)]4], [RuCl2(AsPh3]3], [RuCl2(NBD)]x and [RuCl2(SbPh3)3]. The reactions were carried out in bulk under air atmosphere at 212st.C and 226st.C. Concentration of the complexes corresponded to 58 or 116 ppm of ruthenium. The best results were obtained with [RuHCl(CO)(PPh3)3 as the catalyst. Separation of the catalyst from isomerized oils was accomplished by sorption on diatomaceous earth or on active carbon. The isomerized rapeseed, soybean, sunllower and linseed oils were found to contain respectively 30, 54, 54 and 50 wt-% of conjugated isomers, up to 10 wt-% of polymeric materials and less than 1 ppm of ruthenium.