WO2019042888A1 - Acides nucléiques perfluorés en tant qu'agents tensioactifs de propriétés spécifiques - Google Patents

Acides nucléiques perfluorés en tant qu'agents tensioactifs de propriétés spécifiques Download PDF

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Publication number
WO2019042888A1
WO2019042888A1 PCT/EP2018/072882 EP2018072882W WO2019042888A1 WO 2019042888 A1 WO2019042888 A1 WO 2019042888A1 EP 2018072882 W EP2018072882 W EP 2018072882W WO 2019042888 A1 WO2019042888 A1 WO 2019042888A1
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WIPO (PCT)
Prior art keywords
pfc
perfluorinated
nucleic acids
surfactant
surfactants
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Ceased
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PCT/EP2018/072882
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German (de)
English (en)
Inventor
Konstanze SCHÄFER
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Caperis GmbH
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Caperis GmbH
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Classifications

    • A—HUMAN NECESSITIES
    • A62—LIFE-SAVING; FIRE-FIGHTING
    • A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
    • A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
    • A62D1/0071—Foams
    • A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
    • C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
    • C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
    • C07H19/06—Pyrimidine radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H19/00—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof
    • C07H19/02—Compounds containing a hetero ring sharing one ring hetero atom with a saccharide radical; Nucleosides; Mononucleotides; Anhydro-derivatives thereof sharing nitrogen
    • C07H19/04—Heterocyclic radicals containing only nitrogen atoms as ring hetero atom
    • C07H19/16—Purine radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H21/00—Compounds containing two or more mononucleotide units having separate phosphate or polyphosphate groups linked by saccharide radicals of nucleoside groups, e.g. nucleic acids

Definitions

  • Perfluorinated surfactants have unique properties compared to non-perfluorinated surfactants. They are miscible with neither hydrophilic nor with lipophilic substances. They have an extremely low surface tension and therefore can spread very quickly on surfaces. Perfluorinated areas are chemically inert because the combination of C and F atoms is extremely stable.
  • PFC surfactants which usually have 8 or more perfluorinated C atoms in the molecule.
  • PFC surfactants which usually have 8 or more perfluorinated C atoms in the molecule.
  • Their best known representatives are perfluorooctanesulfonic acid (PFOS) and perfluorooctanoic acid (PFOA).
  • Microorganisms are degraded to the already banned PFC surfactants with 8 perfluorinated C atoms in the molecule, so that it is only a matter of time until they are also subject to the ban.
  • a well-known example is the production of firefighting foam for fire class B, especially for heavy and medium foam.
  • the fire class B includes all liquid, flammable substances and substances that become liquid due to the effect of heat.
  • the liquid substances include, for example, gasoline, oils, fats, paints, varnishes and alcohol.
  • fabrics that melt and become fluid when heated include many plastics, wax, tar, or resins. In case of fire these materials should never be extinguished with water as the water would evaporate and cause deflagration. Here you can use extinguishing foam.
  • Fire-extinguishing foam is a special foam, which consists mainly of air and water and a surfactant-containing foaming agent.
  • PFC surfactants are found primarily in AFFF, AFFF-AR, FFFP, FP and FP-AR.
  • PFC surfactants In contrast to conventional hydrocarbon surfactants, PFC surfactants have a perfluorinated, hydrophobic and lipophobic chain in addition to a polar, hydrophilic group.
  • the polar group makes the molecule water-soluble, while the perfluorinated chain greatly reduces the surface tension and thereby quickly forms a water film. It is helpful that PFCs are not miscible with the burning liquids.
  • Fluorotelomer sulfonic acids or other fluorotelomer surfactants such as 6: 2
  • the background is that up to 10 times the amount must be used when using non-prohibited PFC surfactants (those in the environment to the prohibited PFC surfactants is degraded), it is expected that the Fluortelomertenside be banned promptly.
  • PFC surfactants which are composed of the compounds disclosed herein of nucleic acids or peptides and short-chain perfluorocarbons with Cl to C6.
  • nucleic acids in the sense of this disclosure are RNA, DNA, modified
  • Nucleic acids and peptide nucleic acids are meant.
  • the invention relates in one aspect to a PFC surfactant, in particular for use in the production of fire-fighting foam of fire class B, of the general formula:
  • A is a perfluorocarbon (PFC)
  • B is absent or at least one predetermined breaking point
  • C is absent or a linker or spacer, these being selected from the group consisting of straight-chain or branched acyclic or cyclic,
  • E is an oligonucleotide, a nucleic acid, a modified nucleic acid or an oligonucleotide thereof, a peptide nucleic acid or an oligonucleotide thereof or a peptide chain or an oligopeptide,
  • - F ' is absent or a ligand, wherein the ligand is selected from
  • Group comprising: transferrin, folic acid, galactose, lactose, mannose,
  • G ' is absent or a marker, the marker having a fluorescence Dye is and where:
  • A is selected from the group of perfluorocarbons
  • Alkynes which may be linear or branched, in which all H atoms through
  • the predetermined breaking point B in a particularly preferred manner in the form of a glycosidic bond, a disulfide bridge, an ester group, ether group,
  • nucleic acids are DNA, RNA, modified nucleic acids and
  • modified nucleic acids Meant peptide nucleic acids.
  • modified nucleic acids are LNA (Locked Nucleic Acid), HNA (Hexitol Nucleic Acid) or similar modified ones
  • nucleic acids or peptides at positions accessible thereto, for example at the phosphate group or at the sugar of the sugar-phosphate backbone or at the bases of the nucleic acids or, for example, also at functional groups of the peptide backbone.
  • Perfluorocarbon chains which most preferably contain Cl to C6 and which are known to not accumulate in the organism of higher organisms.
  • the perfluorinated compounds may be Perfluorsiliziumtellen, for example, perfluorinated siloxanes, silicones or silanes, or it can perfluorinated nitrogen or sulfur compounds to be such as NF 3, N 2 F 4, SNF3, CF3SN, SF 4 and SF. 6
  • the novel perfluorinated surfactants disclosed herein are preferably used in aqueous or organic liquids or in mixtures thereof.
  • the Surfactant blends can be composed of both homogeneous PFC surfactant molecule types and heterogeneous surfactant molecule types.
  • PFC surfactant mass concentrations are reached in mixtures which are in the ranges "gas-analogous”, “liquid-expanded”, “liquid-condensed”, or “solid-analogous” or which lead to film collapse, whereby i.a. Vesicles or micelles are formed.
  • PFC surfactants can be used in a variety of ways. Depending on the PFC surfactant concentration used and also on the molecular structure chosen, selfassembling produces PFC surfactant-specific structures that determine the properties of the surfactant-containing mixtures. (Figure 5). Surprisingly, it could be observed that the novel PFC surfactants, in accordance with their mass content in the mixture, also show specific properties, like the prohibited PFC surfactants. Depending on the mass concentrations of the novel PFC surfactants within a mixture, the suitability for certain applications can be predicted
  • Solid-analogous structures of PFC surfactants lead to an impermeability to other molecules at the interface between liquid and air.
  • Fire class 2 responsible for the fact that the burning liquid can secrete little or no flammable vapors over the phase boundary into the surrounding air and the fire is thus contained.
  • novel PFC surfactant component A consists of several interconnected
  • Perfluorohydrocarbon molecules containing Cl - CIO most preferably Cl - C6.
  • Area shield is reinforced by a screen-like structure.
  • a kind of loop is formed by the targeted generation of intermolecular interactions between the molecules of the PF C surfactants and those of the "guest molecules".
  • guest molecules can become entangled in the secondary and tertiary structures of the novel PFC surfactants and, together with these, move from one phase to another. Likewise, these “guest molecules” can be transported from the outside to the cell interior and into the cell nucleus. Due to their strongly negative charge, perfluorinated groups exert intermolecular interactions on OH and other polar groups, which are used here in an advantageous manner.
  • the PFC surfactant is used for transporting "guest molecules" such as nucleic acids, peptides, small molecules, active substances, pharmaceutical substances and other molecules between different phases or into a prokaryotic or a eukaryotic cell or into the cell nucleus .
  • "guest molecules” such as nucleic acids, peptides, small molecules, active substances, pharmaceutical substances and other molecules between different phases or into a prokaryotic or a eukaryotic cell or into the cell nucleus .
  • the surfactant is used in the production of fire - extinguishing foam of fire class B, in the textile and paper industry, in electroplating, as process auxiliaries, in the photo industry, in the plastics industry, in electrical engineering and electronics, in of space travel, as
  • Coolant as a cleaning surfactant, as an emulsifier, in pharmacy, in medicine and in molecular biology.
  • Mass concentration of the PFC surfactant in the mixture has a tool with which you can set the desired PFC surfactant properties exactly.
  • the component E of the PFC surfactant consists of a plurality of interconnected oligonucleotides, nucleic acids, modified nucleic acids or oligonucleotides thereof,
  • both a single shared perfluorocarbon region may be in the molecule as well as the already mentioned above denrimere structure of a plurality of interconnected perfluorocarbon chains or other structures in which several perfluorocarbon molecules are combined.
  • a spacer or linker may be present.
  • the perfluorinated region of the PFC surfactants is composed of a series of cleavable subunits, through which the formation of long PFC chains from the corresponding subunits takes place.
  • the reactions shown here are advantageously carried out on a mixture of different nucleic acids.
  • the advantage here is the formation of a PFC-surfactant mixture of different chain lengths and optionally also different connection variants (position and perfluorinated chain).
  • a homogeneous mixture for example, from similar oligomers of a nucleic acid nucleic acid type may be advantageous.
  • Cycloaddition is an established reaction procedure in which two click reactants react specifically with each other. It is commercially offered by a number of companies. Functionalized perfluorinated compounds with a click component can thus be specifically bound to a nucleic acid.
  • the nucleic acid must have, for example, an alkyne group.
  • the preparation of the functionalized perfluorinated compound with azido group (1H.1H.2H.2H- perfluorooctyl azide) is described below as an exemplary embodiment.
  • R perfluorinated radical with 1-6 perfluorinated C atoms:
  • Peptide nucleic acids are added to the amino acids
  • A, C, G, T represent the bases of the nucleic acids for which
  • the pentamer of DNA (5x adenine) reacts in a nucleophilic substitution with three of its amino groups of adenines with the aldehyde function of 2,3,4,5,6 - pentafluorobenzaldehyde 2. This results in the binding of a hemiaminal.
  • the pentamer of the DNA (5x adenine) reacts with the 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctylphosphonic acid in a condensation reaction and produces a diphosphate ester.
  • the pentamer of the DNA (5x cytosine) reacts with the Fmoc-pentafluoro-L-phenylalanine in a condensation to produce an amide.
  • the pentamer of DNA (5x cytosine) reacts in a nucleophilic substitution with the nonafluoro-tert-butyl alcohol to form the amine.
  • the starting compound 1H, 1H, 2H, 2H-perfluorooctyl iodide 1 was obtained from the company ABCR and subsequently reacted with NaN 3 in DMF at 70 ° C.
  • the reaction mixture was then treated with pentane and water, the phases were separated and the organic phase was dried with MgSO 4. The solvent was removed in vacuo and the resulting crude product analyzed.
  • the detection of the formation of the desired compound was made by chemical shift of the terminal methylene group in the 1H-NMR spectrum.
  • compositions of PFC-surfactant-containing extinguishing foams for fire class B 1) Exemplary compositions of PFC-surfactant-containing extinguishing foams for fire class B:
  • the exemplary composition of the PFC-surfactant-containing extinguishing foam is based on already existing mixtures with the forbidden longer-chain PFC surfactants:
  • Table 1 Content of PFC surfactants in extinguishing foams from different manufacturers.
  • FIG. 1 PFC surfactants in extinguishing foams. Source: http://docplayer.org/45125794-
  • Figure 2 extinguishing foam with PFC surfactant on burning liquid, a water film is generated.
  • Figure 3 extinguishing foam without PFC surfactant on burning liquid without water film.
  • Source Figures 2 and 3: http://docplayer.org/45125794-guide-fluorine-bleach-solvent-selective-and-environmentally-friendly-use.html
  • Figure 4 PFC surfactants in the chrome plating.
  • Source http s: / / www. Wwt- online.de/sites/default/files/fachelle/wwt-modrep-201415-43-47- wienand.indd .pdf
  • FIG. 5 Behavior of PFC surfactants at various concentrations. Source: Akpo, 2005, University of Bergakademiesburg
  • component A of the novel PFC surfactant consists of a plurality of interconnected perfluorohydrocarbon molecules containing Cl-CIO, most preferably Cl-C6.
  • Cl-CIO most preferably Cl-C6.
  • the perfluorinated regions at longer distances and the use of dendrimeric structures of the PFC region (eg by linking several PFC chains) or a bolaform structure with two linking points on the nucleic acid, molecule pockets are formed, embedded in the "guest molecules" and can be transported.
  • the perfluorinated chains usually have a longer linker or spacer. Another function of this molecular structure is that the
  • Area shield is reinforced by a screen-like structure.
  • FIG. 7 In a further embodiment of the invention, a type of loop is formed by the targeted generation of intermolecular interactions between the molecules of the PFC surfactants and those of the "guest molecules".
  • guest molecules can become entangled in the secondary and tertiary structures of the novel PFC surfactants and, together with these, move from one phase to another. Likewise, these “guest molecules” can be transported from the outside to the cell interior and into the cell nucleus. Due to their strongly negative charge, perfluorinated groups exert intermolecular interactions on OH and other polar groups, which are used here in an advantageous manner.
  • the PFC surfactant is used for transporting "guest molecules” such as nucleic acids, peptides, small molecules, active substances,
  • FIG. 8 In a further preferred embodiment of the invention, the component E of the PFC surfactant consists of several interconnected
  • Oligonucleotides nucleic acids, modified nucleic acids or oligonucleotides thereof, peptide nucleic acids or oligonucleotides thereof or peptide chains or oligopeptides.
  • both a single common perfluorocarbon region can be in the molecule as well as the already mentioned above denrimere structure of a plurality of linked together
  • Perfluorocarbon molecules are combined.
  • a spacer or linker may be present.
  • the perfluorinated region of the PFC surfactants is composed of a series of cleavable subunits, through which the formation of long PFC chains from the corresponding subunits takes place.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Health & Medical Sciences (AREA)
  • Biochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Engineering & Computer Science (AREA)
  • Biotechnology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne l'utilisation d'acides nucléiques perfluorés et de peptides perfluorés en tant que composés de propriétés exceptionnelles. Il s'est étonnamment avéré que des composés d'acides nucléiques ou des peptides présentant des perfluorocarbones à chaîne courte en C1 à C6 ont des propriétés exceptionnelles comparables à celles de tensioactifs à base de PFC interdits contenant des perfluorocarbones à chaîne plus longue que C6. Les composés selon l'invention peuvent être dégradés en chaînes perfluorées courtes qui ne sont pas concentrées dans le corps des organismes supérieurs.
PCT/EP2018/072882 2017-08-27 2018-08-24 Acides nucléiques perfluorés en tant qu'agents tensioactifs de propriétés spécifiques Ceased WO2019042888A1 (fr)

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DE102017008214.6 2017-08-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020235658A1 (fr) * 2019-05-21 2020-11-26
WO2021060506A1 (fr) * 2019-09-27 2021-04-01 Ａｇｃ株式会社 Acide nucléique contenant un groupe alkyle perfluoré et son procédé de production

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006081035A2 (fr) * 2004-12-30 2006-08-03 Berry & Associates, Inc. Reactifs oligonucleotidiques fluoritiques et purification par affinite d'oligonucleotides
WO2012130941A2 (fr) * 2011-03-31 2012-10-04 Schaefer Konstanze Composés perfluorés pour le transfert non viral d'acides nucléiques

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
WO2006081035A2 (fr) * 2004-12-30 2006-08-03 Berry & Associates, Inc. Reactifs oligonucleotidiques fluoritiques et purification par affinite d'oligonucleotides
WO2012130941A2 (fr) * 2011-03-31 2012-10-04 Schaefer Konstanze Composés perfluorés pour le transfert non viral d'acides nucléiques

Non-Patent Citations (3)

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Title
CHRISTIAN BELLER AND WILLI BANNWARTH: "Noncovalent Attachment of Nucleotides by Fluorous-Fluorous Interactions: Application to a Simple Purification Principle for Synthetic DNA Fragments", HELVETICA CHIMICA ACTA, VERLAG HELVETICA CHIMICA ACTA, CH, vol. 88, 1 January 2005 (2005-01-01), pages 171 - 179, XP002478874, ISSN: 0018-019X, DOI: 10.1002/HLCA.200490291 *
HOLZBERGER B ET AL: "Enzymatic synthesis of perfluoroalkylated DNA", BIOORGANIC & MEDICINAL CHEMISTRY, PERGAMON, GB, vol. 17, no. 10, 15 May 2009 (2009-05-15), pages 3653 - 3658, XP026090837, ISSN: 0968-0896, [retrieved on 20090407], DOI: 10.1016/J.BMC.2009.03.063 *
WILLIAM H PEARSON ET AL: "Fluorous Affinity Purification of Oligonucleotides", JOURNAL OF ORGANIC CHEMISTRY,, vol. 70, no. 18, 1 January 2005 (2005-01-01), pages 7114 - 7122, XP002478873, ISSN: 0022-3263, [retrieved on 20050802], DOI: 10.1021/JO050795Y *

Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPWO2020235658A1 (fr) * 2019-05-21 2020-11-26
WO2020235658A1 (fr) * 2019-05-21 2020-11-26 株式会社四国核酸化学 Blocmère multifluoré utilisé dans la synthèse d'oligonucléotides et procédé de synthèse d'oligonucléotides l'utilisant
KR20220002469A (ko) * 2019-05-21 2022-01-06 나티아스 인크. 올리고뉴클레오티드 합성에 사용하는 멀티플루오로스블록머 및 이를 사용한 올리고뉴클레오티드 합성방법
CN113924309A (zh) * 2019-05-21 2022-01-11 株式会社纳蒂亚斯 寡核苷酸合成中使用的多氟嵌段聚体以及使用其的寡核苷酸合成方法
JP7393807B2 (ja) 2019-05-21 2023-12-07 株式会社ナティアス オリゴヌクレオチド合成に用いるマルチフルオラスブロックマーおよびこれを用いたオリゴヌクレオチド合成方法
KR102692448B1 (ko) 2019-05-21 2024-08-05 나티아스 인크. 올리고뉴클레오티드 합성에 사용하는 멀티플루오로스블록머 및 이를 사용한 올리고뉴클레오티드 합성방법
US12559516B2 (en) 2019-05-21 2026-02-24 Natias Inc. Multi-fluorous blockmer for oligonucleotide synthesis, and oligonucleotide synthesis method using the same
WO2021060506A1 (fr) * 2019-09-27 2021-04-01 Ａｇｃ株式会社 Acide nucléique contenant un groupe alkyle perfluoré et son procédé de production
JPWO2021060506A1 (fr) * 2019-09-27 2021-04-01
CN114514236A (zh) * 2019-09-27 2022-05-17 Ａｇｃ株式会社 含有全氟烷基的核酸及其制造方法

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