MXPA99005480A - Non-helical supramolecular nanosystems - Google Patents
Non-helical supramolecular nanosystemsInfo
- Publication number
- MXPA99005480A MXPA99005480A MXPA/A/1999/005480A MX9905480A MXPA99005480A MX PA99005480 A MXPA99005480 A MX PA99005480A MX 9905480 A MX9905480 A MX 9905480A MX PA99005480 A MXPA99005480 A MX PA99005480A
- Authority
- MX
- Mexico
- Prior art keywords
- oligomer
- further characterized
- supramolecular
- supramolecular nanosystem
- nanosystem according
- Prior art date
Links
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- 238000012546 transfer Methods 0.000 description 1
- FTVLMFQEYACZNP-UHFFFAOYSA-N trimethylsilyl trifluoromethanesulfonate Chemical compound C[Si](C)(C)OS(=O)(=O)C(F)(F)F FTVLMFQEYACZNP-UHFFFAOYSA-N 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Abstract
The invention relates to a supramolecular nanosystem containing at least one substantially non-helical oligomer (oligomer A) and one or more identical or different, substantially non-helical oligomers which do not pair with each other, with identical or different functional units (oligomer B), in which the oligomer A can pair specifically non-covalently, and oligomer B is determinable by its monomers.
Description
NON-HELICAL SUPRAMOLECULAR NANOSYSTEMS
DESCRIPTIVE MEMORY
The present invention relates to a supramolecular nanosystem, which contains at least one essentially non-helical oligomer (oligomer A) and one or more identical or different oligomers, essentially non-helical and not coupling with each other, with functional units. different oligomers (oligomer B), wherein the oligomer A can be coupled to the oligomer B in a specifically non-covalent manner and the oligomer B can be determined by its monomers. Meanwhile, the miniaturization of technical constituent elements advances in the field of molecular orders of magnitude. The production of miniaturized electronic elements integrated by means of conventional methods, such as by means of a photochemical treatment of a constituent component, is also determined by the respective chemical and physical properties of the materials used. In the nanodomain, the different or atomically quantized molecular properties can be used to create completely new constituent components. The properties of the materials, which are caused or affected by the nanostructuring, are above all the optical or quiropropic properties, for example in the Kerr cells or in the LEP technique;
electrical properties, for example in semiconductors or conductors by means of the constitution of conduction bands, electrons in defect, centers of color or domains with modulatable tunnel currents; chemically catalytic properties, as for example in zeolites, catalysis of metal agglomerates, constitution of reaction spaces; as well as physical properties of surface and transport such as permeability, adhesion and compatibility with other materials or sensitive biological systems (biocompatibility). In supramolecular chemistry, the described nanomolecular properties are selectively used to create completely new materials, which can be organized by themselves in the form of coupling systems. The coupling systems are supramolecular systems of non-covalent interaction, which excel by selectivity, stability and reversibility, and because their properties are preferably affected thermodynamically, ie for example by temperature, pH value and concentration. DNA and RNA play a fundamental role in this case as carriers of hereditary factors. Such coupling systems can be used for example, by virtue of their selective properties, also as "molecular adhesive material" for the concentration of different agglomerates of metals for the assembly of agglomerates with potentially new properties [Mirkin, C.A. and others, Nature, 1996, 382, 607-9, Alivisatos, A.P. and others, Nature, 1996, 382, 609-11). The coupling or hybridization properties of the DNA present in nature were used to couple the metal agglomerates attached to the DNA strand with a complementary DNA strand. In this way, connections of agglomerates with potentially new properties of the materials were achieved. Such supramolecular nanosystems can therefore be considered as "molecular machines" or functional "molecular elements". Strong and thermodynamically controllable coupling systems play an increasingly important role for use in the field of nanotechnology, for the production of new materials, diagnostics, therapeutics, as well as new constituents microelectronic, photonic, optoelectronic, and for the controlled concentration of molecular species by supramolecular units. For the production of such coupling systems, the constituent elements of the DNA or RNA have the following disadvantages: a) The forces that hold together two chains, especially hydrogen bonds and stacking effects, they are very small according to nature. Such applications therefore exhibit a small stability. This can easily be determined by including a so-called transformation curve and the determination of the transformation point. Accordingly, relatively long simple chains are necessary for the reproduction of coupling systems, which results in the predominance of the portion of the coupling system of the supramolecular unit, ie the "nucleotide loading" is high. b) Through the formation of Hoogsteen couplings, which are alternatively possible to the Watson-Crick couplings, the selectivity decreases. This often involves parallel duplications or irreversible coupling processes. c) By means of the high flexibility of the structure of the sugar and phosphate base, helical conformations are developed, by means of which the spatial disposition in supramolecular units can be controlled less well. d) It is not necessary to exclude a possible interference with the genetic material of biological systems, if the supramolecular units come into play in a biological system, that is, an octagonality of the coupling process is missing. Then, it is simply difficult to make use of the constitutive components of DNA or RNA, for example in the two-dimensional and three-dimensional supramolecular structure joined together (see for example W096 / 13522) in a physiological medium especially with reference to point (d. The mission of the present invention was therefore to find a system which will avoid as much as possible one or more of the disadvantages described.
It was thus surprisingly discovered that supramolecular, essentially non-helical nanoslides have particularly advantageous constitutive components. An object of the present invention is therefore a supramolecular nanosystem, which contains an essentially non-helical oligomer (oligomer A) and one or more identical or different oligomers, essentially non-helical and not coupling with each other, with functional units. different oligomers (oligomer B), in which the oligomer A can be coupled to the oligomer B in a specifically non-covalent manner and the oligomer B can be determined by its monomers. Non-covalent coupling in the sense of the present invention means an association of the oligomer A with the oligomer B through non-covalent interactions, such as, for example, hydrogen bonds, salt bridges, "stacking", formations of compounds with metals, complexes of load and transfer and hydrophobic interactions. Determinible in the sense of the present invention means that the functional unit is directed, ie encoded, by the oligomer. The code is defined by the previously fixed series and the class of monomers. This can be for example a certain sequence of nucleotides. The class and the series of monomers of the oligomer B define the class and the series of monomers of the oligomer A. In the case of the nucleotides, these are the complementary nucleotides to each other respectively (see for example figure 2).
In a special embodiment, the oligomer A can be coupled with both the oligomer B and itself with the shape of a hairpin curve for hair. Depending on the external conditions, the structural modifications by means of the present can easily be made macroscopically inductible and determinable (see for example Figure 4). By way of example, structural modifications of the molecular system according to the invention can be originated by means of a modification of the equilibrium conditions, such as, for example, the concentration of oligomer B, the salt concentration, the pH value, the pressure and / or temperature. By regulating certain equilibrium conditions, different domains can also be produced for coupling or uncoupling, so that reversible molecular residues (the so-called nano transport) can be placed in close proximity. In a preferred embodiment, it is treated in the case of the essentially non-identical oligomer of a pentopyranosyl nucleic acid, in particular of a ribo-, arabino-, lixo- and / or xylo-pyranosyl-nucleic acid, preferably of a ribopiranosyl acid -nucleic, also called RNA-pyranosyl (p-RNA). The p-RNA as an example of a pentopyranosyl nucleic acid is a nucleic acid, which contains ribopyranose instead of RNA rhizobiosane as constituent component of sugar and therefore forms exclusively Watson-Crick-coupled, antiparallel, reversible duplications, "meltable", almost linear and stable. In addition, there are homochiral p-RNA chains of opposite sense of chirality, which are also controllably coupled and are not strictly helical in the duplication formed. This valuable specific character for the construction of supramolecular units is related to the relatively small flexibility of the ribopyranose phosphate base structure as well as to the strong inclination of the plane from the base to the chain axis and the tendency caused by this to the stacking of bases in the resulting duplication and can be redirected to the participation of a 2 ', 4'-cis-disubstituted ribopyranose ring in the construction of the base structure. By virtue of the high selectivity and stability as well as the formation of strictly linear double chains in the planar aspect, pentopyranosyl nucleic acid and preferably p-RNA is especially preferred for the present invention. All the residues, which are similarly linked to the pentaplranosyl chain, are on the same side of the duplication, which is especially advantageous. Pentapyranosyl nucleic acids can be produced, for example, according to Eschenmoser et al. (Helv. Chim. Acta 1993, 76, 2161; Helv. Chim Acta 1995, 78, 1621, Angew Chem. 1996, 108, 1619-1623) and are generally configured to the right or to the left. For the production of the supramolecular system according to the invention, it serves as a natural model the decoding of amino acids for the synthesis of protein by means of the respective triplets of bases as anticodon (see Figure 1). Analogously to this, functional units identical or different to an oligomer of defined structure are joined according to the present invention. For example, a pentopyranosyl oligonucleotide, which is modified at the 3 'and / or 5' end with free sulfhydryl groups, is bound to gold particles converted to monomaleimido derivatives
(analogously to Alivisatos, A.P. and others (1996), previous). With the oligomer thus modified (the so-called oligomer B), an oligomer A complementary to it is brought into contact for coupling, so that the supramolecular system according to the invention can be formed. The double chains that are formed are generally present in essentially flat / linear form, which is especially advantageous. In general, oligomer A is longer than oligomer B. A length of oligomer A of from about 10 to about 500, preferably from about 10 to about 100, monomer units is especially preferred. The oligomer B is generally from about 4 to about 50, preferably from about 4 to about 25, in particular from about 4 to about 15, especially from about 4 to about 8 monomer units in length. In another embodiment, the portion of pentopiranosil pentopiranosilo-nucleic acid may be modified so thiophosphate, alkylated phosphate, phosphonate and / or amide (see for example Uhlmann E. and Peyman A. (1990) Chemical Reviews, 90, 543- 584, No. 4). In another embodiment of the present invention it is used for encoding the oligomers of the canonical nucleobases adenosine, guanosine, cytosine, thymidine and / or uracil or also isoguanosine, isocltosina, 2,6-diaminopurine and / or xanthine. In the cases mentioned last, the complementary bases are present in the form of isoguanine / isocytosine pairs or 2,6-diaminopurine / xanthine. In addition, adenosine is generally coupled with thymidine or uracil and guanosine with cytosine. In another embodiment, non-covalent coupling between the oligomer A and the oligomer B can take place by means of a chelator.
For example, the nucleobases of a pentopyranosyl nucleic acid are replaced by the chelator. For this purpose, for example, chelating agents that are derived from pirasolilpyridine or pyridokinesoline are suitable. In the absence of a metal ion, for example Cu2 or Ni2, the complex formation takes place and therefore the specific coupling between both oligomers (see Figure 3). As the functional unit of the oligomer B, a metal is generally suitable, preferably an agglomerate of metals, in particular a noble metal, especially gold, silver and / or platinum. Semiconductor compounds are also suitable, such as, for example, cadmium selenide and / or cadmium sulfide. In addition, a peptide, which can be linked to the oligomer through an appropriate linker, for example N-phthaloylaminoethyluracil or N-phthaloyltriptamine, is suitable as the functional unit. Another functional unit is for example an oxidation / reduction center, that is to say an electron donor or acceptor, for example a quinone or hydroquinone. Also suitable are fluorescence labels, for example fluorophores and / or chromophores, such as, for example, benzoquinones or azobenzoles. Other functional units may represent a chelator, which is derived preferably antrocianógenos, polioxicarboxíllcos acids, pollaminas, dimethylglyoxime, ethylenediaminetetraacetic acid and / or nitrilotriacetic acid, or also conductive oligomers, such as conjugated compounds of alkyne-alkene-aromatic. The linkage of an oligomer with a functional unit, which results in oligomer B, can be carried out in general with linkers known to those skilled in the art (see for example Mirkin CA et al. (1996), Nature, 382, 607 -609, Alivisatos, AP et al. (1996), mentioned above, Dawson, PE et al. (1994), SBH Kent Science, 30, 776-779, Liu C.-F. et al. (1996), 116, 4149- 4153) or with commercial linkers of amldite bases (Wei Z. and others, Bloconjugate Chem. (1994), 5, 468-474, Liu C.-F. and others (1994), Proc. Nati. Acad. Sel. USA, 91, 6584-6588). The oligonucleotides themselves can for example be produced automatically in an oligonucleotide synthesizer. In another modality, the oligomer A can be linked to the oligomer B by association, ie it can be fixed. Chemical fixation is preferred, for example covalent crosslinking, metathesis, coupling at the rear ends, Michael addition of thiols and / or oxidation formation of disulphide bridges. It is especially preferred if the supramolecular system according to the invention is produced on a solid phase, for example a so-called substrate or base. Suitable base materials are, for example, ceramics, metal, in particular noble metal such as gold, silver or platinum, glasses, plastics, crystalline materials or thin layers of the substrate, in particular of the named materials, or (bio) molecular filaments, as cellulose or support proteins. Substrate formation generally occurs covalently, almost covalently, supramolecularly or physically, as well as magnetic
(Shepard, A.R. (1997) Nucleic Acids Res., 25.3183-3185, No. 15), in the electric field or through a molecular sieve. For example, oligomer A can be synthesized directly to the substrate position or can be bound to certain positions on the substrate. Examples of conjugation and substrate formation methods by means of periodate-oxidation and reductive amination of Schiff's base, N-hydroxysuccinimide ester, preferably of bicarboxylic acid linkers, ethylene diamine phosphomidate linkers, for example mercapto, iodacetyl processes and maleinimide and / or covalent or non-covalent methods with biotin linkers. Another embodiment of the present invention is a library containing several different supramolecular nanosystems according to the invention. It is particularly advantageous if the library is constructed combinatorially. A combinatorially constructed library is suitable for example for the selection of properties, while coupling a statistically produced (sub) library or conforming combinatorial techniques of deconvulsion to the complementary oligonucleotide (see for example Wilson-Linguardo (1996) J.med.Chem ., 39.2720-2726).
For the case in which the functional unit of the oligomer B is for example a metal agglomerate, a combinatorially prepared library is especially suitable for the search for catalysts. For this, for example, the oligomer A is synthesized combinatorially and is coupled with several different oligomers B with different agglomerates of metals as functional units. In this way, a so-called agglomerate library is obtained, whose diversity correlates directly with that of oligomer A. Preferably, the routines with (sub) libraries are suitable here, which allow a simple identification of the active species, such as positional exploration or orthogonal libraries. The agglomerate library can then be investigated for its homogeneous catalytic properties, for example in water, for the catalysis of vinyl acetate monomers. In general and in particular for the production of libraries, it is advantageous if the pentopyranosyl nucleic acid contains a relatively high portion of cytosine and guanosine, since by virtue of the higher enthalpy of binding of this pair of nucleotides, compared to the Adenosine or thymidine, shorter oligonucleotides can be used, whereby the "nucleotide loading" of the supramolecular nanosystem can be decreased according to the invention. By substituting the nucleobases by means of one or more identical or different chelators, as described above in more detail, the "nucleotide loading" can be further reduced. In this way, complexes of a single center are formed, which form linear, non-helical, oligomeric metal complexes. By virtue of the arrangement in the form of steps in a plane, the coupling method can react optimally on the extension of different metal centers. The applications thus formed have in general an inclined structure, however non-helical, repetitive, which coordinates respectively according to the selection of the ligand specific metal stents and makes possible along the axis of the duplication metal-metal interactions and defective points desired. In this way, metal sequences can be produced, which represent a new alloy nanolote for the production of the so-called "nanowires". With the supramolecular nanosystems according to the invention described above, it is also possible to locate, for example, different agglomerates of metal with reference to the construction of electronic connection samples on the supramolecular plane (see for example Kubiak CP (1996) Science, 272, 1323-1325). It is also possible in the construction of the so-called gratings of agglomerates with dithioles in the form of rods, which exhibit good stability (see, for example, Andrés R.P. and others (1996) Science, 273, 1690-1693, Schiffrin D.J., et al. (1995) ADV Mat., 7, 795-797). The supramolecular nanosystem according to the invention which has been described possesses especially good stability and selectivity and is particularly suitable for self-organization. It also has a controllable topicality and aggregation or self-organization has especially good dynamic self-influence. The fields of application are therefore particularly in the production of electronic components, such as for example information storage media, diagnostic probes or photoelectronic constituents; catalysts; semiconductors; photochemical units; materials or biocompatible units or functional microphotes. The following figures and examples should explain the invention in more detail, without limiting it in this way.
DESCRIPTION OF THE FIGURES
Figure 1 is a schematic representation of the natural coupling of bases in the synthesis of peptides. Figure 2 is a schematic representation of a supramolecular nonosystem according to the invention with nucleobases adenosine (A) and thymidine (T) and different functional units designated as x1 to x1 (coding units).
Figure 3 is a schematic representation of a chelator complex of a center through a pyrido [3,2-h] quinazolin-2 (1) -one as a chelator. Figure 4 is a schematic representation of a balance reaction between a curve of hairpin and a duplication. Figure 5 is a section of an x-ray structure analysis of a complex of nickel chelator, rlbopyroose and pyrazolylpyridine.
EXAMPLES
EXAMPLE 1 PRODUCTION OF AN ACID (GOLDED AGGLOMERATE) -PIRANOSIL- RIBONUCLEIC
RNA-pyranosyl was produced according to Eschenmoser and others
(mentioned above) by means of a synthesis of phosphoamidite. A chain was joined by gold agglomerations, as described in Mirkin C.A. and others (1996), mentioned above. The complementary strands of a pH buffer solution (1 M NaCl, 10 mM trisol HCl, pH7) were found at 0 ° C (see Figure 2).
EXAMPLE 2 PRODUCTION OF A SELF-COMPLEMENTARY OLIGONUCLEOTIDE OF
THE ITGGCCA SEQUENCE
The automatic solid phase synthesis of the oligonucleotide with the ITGGCCA sequence was carried out, as described by Pitchs S. et al. (1993) Helv. Chim. Act 78, 1621-1635. The performance on an Ecosyn D300 + automatic synthesizer from Eppendorf was an average of 93.2%. The coupling times amounted to 45 minutes, the oxidation rate to 2 minutes and the detrity time to 7 minutes with circulating dichloroacetic acid. After synthesis, the oligonucleotide was deprotected with tetraqulsphenylphosphinpalladium (20 mg for one μmol of substrate supplement) with addition of 20 mg of diethylammonium acid carbonate and 20 mg triphenylphosphine for five hours at room temperature, then washed with acetone and water and treated for 45 minutes with solution of said fresh aqueous sodium carbamate. The product was then dissociated by means of a 24% hydrazine hydrate solution, at 4 ° C, for 24 hours, with stirring. The elimination of salts took place in a Reverse-Phase-Sep-Pak cartridge and the purification by means of RP-CLAR (RP-18, water / acetonitrile gradient, pH7). Subsequently, the salts were removed and lyophilized again, by means of which the product "Trityl-on" was obtained. This was deprotected with 80% formic acid, evaporated, taken up in 10 ml of water, extracted against dichloromethane and evaporated again by means of HPLC. 8 OD of the desired product were obtained. The mass spectrometric analysis gave the following result:
Samples: LX626-1: MS-Nr: 970523 Problem statement: Spectrometric mass characterization of the sample
Mass spectrometer: TSQ 700 (Flnnigan / mat) Measuring conditions: EM; spray pump Ionization: Electrospray ionization (IEA) Results: The mass aspectrum showed a molecular mass M = 2242.
EXAMPLE 3 MOLECULAR NANOCINEMATICS
With the help of the phosphoamidite method, a partially self-complementary RNA-pyranosyl chain was synthesized as a hairpin with the 4 'and 5' linker ends of the linker-pr-GCGA5CGC-linker sequence and ligated at the linker ends as describes Alivisatos, AP and others (1996), mentioned above, with maleimido-agglomerations of gold. Then, it was determined spectroscopically in the normal pH regulator (0.15 m NaCI or 1 M NaCl, 10 mM Tris-HCl, pH 7) in coupling with the hairpin of the product at 10 mM. The addition of an equivalent of the complementary chain pr-G (T5) C showed spectroscopically the opening of the hairpin and the dissolution of the gold agglomerate. The simple dilution of the solution caused the hairpin structure to reproduce. In this way, a controlled substrate can be exposed macroscopically by means of dilution to different reaction centers (see Figure 4).
EXAMPLE 4 SYNTHESIS OF A PIGIDIL-PIRAZOL-RIBONUCLEIC ACID LIQUID AS A MONOMER FOR OLIGOMERIC LIGANDS
The following reaction scheme shows the production of 2- [7- (2 ', 3', 4'-Tri-O-benzoyl-1'ß-ribopyranose) pyraz-9-yl] pyridine:
Representation of 2-r7- (2 ', 3', 4'-tri-O-benzoyl-1'ß-ribopyranose) pyrazole-9-illpyridine
0.50 g (3.44 mmol) of 2- [3 (5) -pyrazoloyl] plridine was dissolved in 30 ml of CH2Cl2 and cooled to -15 ° C. 2.30 g of 2 ', 3', 4'-tri-0-benzoyl-1'-trichloroimidate-D-ribopyranosyl were added dropwise in
ml of CH2Cl2. The solution became light yellow. After that, 0.8 ml (1.2 Equiv.) Of TMSOTf in 15 ml of CH2Cl2 was added dropwise at -15 ° C within 15 minutes. The solution became cloudy and a white sediment formed. The solution was stirred another 5 hours between -10 ° C and + 5 ° C.
After that, the solution was filtered off and concentrated. Purification of the product took place by flash chromatography on silica gel (CH2Cl2 / acetone 95/5). 1.77 g (3 mmol, 87%) of the product. Retention factor: 0.47 (CH2 / CI2 / acetone to 9/1) P.F .: 91-93 ° C (CH2CI2 / lsohexane). UV (CH3CN)? = 202 nm'1 e = 21522? = 230 nm "1 e = 35826? = 274 nrtf1 e = 7696 1 H NMR: d (ppm) = 8.60 (DM, J = 4.8 Hz, 1 H, 6-H); 8.07 (d, J =
8. 5 Hz, 2H, 2 o-benz.-2 '); 7.98 (d, J = 7.8 Hz, 1 H, H-3), 7.93 (d, J = 8.3 Hz, 2H,
2-o-benz.-3'ó 4 '); 7.82 (d, J = 8.3 Hz, 2H, 2 o-benz.-3 'or 4'), 7.77 (d, J = 2.6 Hz,
1H, H-11); 7.70 (td, J = 7.6 u, 1.8 Hz, 1H, H-4); 7.62 (t, J = 7.5 Hz, 1H, p-benz-4 '), 7.52 (t, J = 7.5 Hz, 1 H, p-benz-3'); 7.48 (t, J = 7.5 Hz, 2H, 2.m-benz.-4 '),
7. 46 (t, J = 7.5 Hz, 1H, p-benz.-2 '), 7.34 (t, J = 7.8 Hz, 2H, 2-m-benz.-3'); 7.25
(5, J = 7.7 Hz, 2H, 2.m-benz.-2 '), 7.19 (ddd, J = 7.6, 4.8 u. 1.8 Hz, 1 H, H-5);
6. 99 (d, J = 2.6 Hz, 1H, H-10), 6.49 (t, J = 3 1 Hz, 1H, H-3 '), 6.17 (d, J = 6.8
Hz, 1 H, H-1 '); 6.11 (dd, J = 6.8 u, 3.1 Hz, 1 H, H-2 '); 5.69 (m, 1 H, H-4 '), 4.32 (dd, J = 11.2 u 8.2 Hz, 1 H, H-5'), 4.28 (dd, J = 11.2 or 8.2 Hz, 1 H, H- 5'). The coordination of the signals took place with the help of a 1H, 1H-COZY spectrum.
13 C NMR: d (ppm) = 165.23 (CO-4 '); 165.17 (CO-3 ');
164. 88 (CO-2 '); 152.85 (C-2); 151, 51 (C-9); 149.16 (C-6); 136.62 (C-4); 133.50 (C-p-benz.-4 '); 133.35 (C-p-benz.-3 '); 133.32 (C-p-benz.-2 '); 130.44 (C-11); 129.79 (2-C.o-benz.-4 '); 129.78 (2.C-o-benz.-3 '); 129.73 (2 C-o-benz.-2 '); 129.37 (C-i-benz.-4 '); 129.11 (C-i-benz.-3 '); 128.78 (C-i-benz.-2 '); 128.61 (2.C-m-benz.-4 '), 128.337 (2.C-m-benz.-3'), 128.24 (2.C-m-benz.-2 '), 122.75 (C-5); 120.47 (C-3); 105.97 (C-10; 85.42 (C-1 '); 68.57 (2C-2' or 3 '); 66.97 (C-4'); 63.85 (C-5 '). The coordination of the signals took place with of a 1H, 13C-COZY, NOESY NOE spectrum between H-11 and H-1 ', H-2': Check of the C-1 'link to N-7 EM: Electrospray ionization (IEA) [MH *] = 590 C34 H27 N3 O7 M = 589 Analysis of the X-ray structure of the monomer crystals checked the correct glycosidic bond after recrystallization of CH2Cl2 / lsohexane.The benzoylated monomer already shows after treatment with alcohol chloride-hydrate solution. nickel (II) (reflux) the desired properties of complex formation (UV, NMR) This result was confirmed by means of an X-ray structure analysis of the nickel chelate complex, riboplranose and pyrazolylpyrrolidine (Figure 5). shows the equivalent of the coupling nucleobase by means of a strong nitrogen back-linking ligand.The monomer thus known can be transferred and Rotected in the form of D-enantiomer, as already described above to the p-phosphoamidite RNA.
Claims (24)
1. - Supramolecular nanosystem, which contains at least one essentially non-helical oligomer (oligomer A) and one or more identical or different oligomers, essentially non-helical and not coupling with each other, with identical or different functional units (oligomer B ), further characterized in that the oligomer A can be coupled to the oligomer B in a specifically non-covalent manner and the oligomer B can be determined by means of its monomers.
2. Supramolecular nanosystem according to claim 1, further characterized in that the oligomer A can form a hairpin curve for hair.
3. Supramolecular nanosystem according to claim 1 or 2, further characterized in that the essentially or helical oligomers A and B are pentopyranosyl nucleic acid.
4. Supramolecular nanosystem according to claim 3, further characterized in that the pentopyranosyl nucleic acid is a ribo-, arabino-, lixo- and / or xyl-p-pnosyl-nucleic acid, preferably a ribopyranosyl-nucleic acid.
5. Supramolecular nanosystem according to claim 3 or 4, further characterized in that the pentopyranosyl portion of the pentopyranosyl nucleic acid is configured to the right or to the left.
6. Supramolecular nanosystem according to one of claims 3-6, further characterized in that the non-helical oligomer A has a length of from about 10 to about 500, preferably from about 10 to about 100, monomer units.
7. Supramolecular nanosystem according to one of claims 3-6, further characterized in that the non-helical oligomer B has a length of from about 4 to about 50, preferably from about 4 to about 25, in particular from about 4 to about 15, especially about
4 to about 8 monomer units.
8. Supramolecular nanosystem according to one of claims 3-7, further characterized in that the pentapyranosyl portion of pentapyranosyl nucleic acid is in the form of a thiophosphate, alkylated phosphate, phosphonate and / or amide.
9. Supramolecular nanosystem according to one of claims 3-8, further characterized in that the nucleic acid contains as nucleobase adenosine, guanosine, soguanosine, cytosine, isocytosine, thymidine, uracil, 2,6-diaminopurine and / or xanthine.
10. - Supramolecular nanosystem according to one of claims 3-9, further characterized in that the nucleobase is replaced by a chelator.
11. Supramolecular nanosystem according to claim 10, further characterized in that the chelator is derived from pirasolilpyridine and / or pyridoquinazoline.
12. Supramolecular nanosystem according to one of claims 1-11, further characterized in that the functional unit is selected from a metal, preferably an agglomerate of metals, a semiconductor compound, a peptide, an oxide-reduction center, a fluorescence label, a chelator and / or a conductive oligomer.
13. Supramolecular nanosystem according to claim 12, further characterized in that the metal is a noble metal, in particular gold, silver and / or platinum.
14. Supramolecular nanosystem according to claim 12, further characterized in that the semiconductor is selected from cadmium selenide and / or cadmium sulfide.
15. Supramolecular nanosystem according to claim 12, further characterized in that the fluorescence label is a fluorophore and / or a chromophore.
16. Supramolecular nanosystem according to claim 12, further characterized in that the chelator is derived from antrocyanogens, polyoxycarboxylic acids, polyamines, dimethylgoximes, ethylenediaminetetraacetic acid and / or nitroltriacetic acid.
17. Supramolecular nanosystem according to one of the claims 1-16, further characterized in that the oligomer A is linked to the oligomer B by association. 18. - Library containing several different supramurcular nanosystems according to one of claims 1-17. Process for the production of a supremolecular nanosystem according to one of claims 1-11 or a library in accordance with the claim 18, further characterized in that the oligomer A is specifically and non-covalently coupled to one or more identical or different oligomers B, under appropriate conditions. 20. Method according to claim 19, further characterized in that in another step the oligomer A is linked with the oligomer (s) B. 21.- Procedure for the structural modification of the supramolecular nanosystem in accordance with one of The claims
1-16, further characterized in that the equilibrium conditions are modified. 22. Method according to claim 21, further characterized in that the concentration of oligomer B, the salt concentration, the pH value, the pressure and / or the temperature are modified.
23. - Use of a supramolecular nanosystem according to one of claims 1-17 as an electronic constituent component; catalyst; semiconductor; photochemical unit; material or biocompatible unit or functional microprosthesis. 24.- Use of a library in accordance with the claim
18 for the detection of a metal catalyst.
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DE19651560.2 | 1996-12-11 | ||
EPEP97/06907 | 1997-12-10 |
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