Functionalised nanoparticles, preparation and use thereof

FIELD: chemistry.

SUBSTANCE: invention relates to stable complexes consisting of metal oxides - iron, cobalt or alloys thereof in form of nanoparticles and bifunctional compounds, where the bifunctional compounds are selected from thiols, carboxylic acids, hydroxamic acids, phosphoric esters or salts thereof, having an aliphatic chain containing a second functional group in the terminal position ω, which can be used in certain novel hydrophilic plates and fibres, as well as a method of producing complexes. The method involves reaction of dispersion of said nanoparticles in an organic solvent with a suitable binder. The mixture is stirred for several hours at low temperature and the obtained product is then cooled and separated by centrifuging, and can then be cleaned via repeated dispersion in a suitable solvent and repeated deposition.

EFFECT: novel complexes with improved solubility in water-alcohol medium are obtained.

13 cl, 3 dwg, 9 ex

 

The technical field.

The present invention relates to the field of functionalized nanoparticles, their preparation and application.

The prior art to which the invention relates.

It is known that some organic molecules can adsorb on the surfaces of solid inorganic materials, and this property is widely used in such an extent that the formed whole classes of technologically important compounds, such as dispersants and wetting agents.

Some of these molecules are not only adsorbed mentioned surface, but also contribute to the formation of compact structures that can deeply change its properties.

Typical examples of organic molecules above-mentioned type (hereinafter referred to as a binder) are simple monofunctionalized aliphatic compounds such as thiols, dodecylphosphonic sodium bromide, cetyltrimethylammonium, various aliphatic phosphates and phosphonic, carboxylic and hydroxamic acids.

The interaction usually takes place between a single functional group and a metal inorganic surface, leaving, therefore, free simple aliphatic chain, which in no way able to interact with other functional molecules.

The affinity between organic the ski molecules and surfaces depends on the chemical nature of each of them: these interactions have been studied for some very well-known cases, however, a full understanding of the different affinity binders with nanoparticles are still there, the issue is discussed in academic circles, because the results are often contradictory.

It is also known that nanoparticles are materials with a size less than 500 nm, or, according to some authors, less than 100 nm, which can form a stable dispersion in liquids, if between the individual particles there is the potential repulsion. In the dispersion is not observed no precipitation, because inherent in the particles provided by the temperature movement prevents them from settling under the action of gravity. The interaction potential between two particles depends primarily on the condition of the surface of the nanoparticles and it may change as a result of adsorption or chemical binding with other molecular or ionic particles present in solution.

Known for some of the complexes formed by nanoparticles and monofunctional binding of the type specified above [see, for example, Aronoff Y.G. et al., J. Am. Chem. Soc. 1997, 119, 259-262; Heimer T.A., de Arcangelis et al., Langmuir, 2002, 18, 5205-5212; C. Yee et al., Langmuir, 1999, 15, 7111-7115; Folkers et al., Langmuir, 1995, 11, 813-824], but they have various disadvantages.

Not to mention the scarcity of the studied material and a binder, the above products are insoluble in aqueous-alcoholic medium, which is a very VA the essential condition for biomedical and pharmacological applications. Along with this, the remaining free simple aliphatic chain are completely unable to interact with functional groups typically present in bioactive molecules.

Considering the above, of course, it is important to have the complexes formed by the nanoparticles and functional binder, which would make them suitable for different desired goals, eliminating the above disadvantages.

Brief disclosure of the invention.

Stable complexes can be obtained by binding the nanoparticles of various types of oxides of transition metals with mono - and bifunctional compounds.

A brief description of the drawings.

Figure 1 schematically illustrates the methods of preparation of complexes formed nanoparticles with the above-described bifunctional binder, and the subsequent reactions of these complexes with biopolymers, molecules (cyclodextrins, antibodies etc) and proteins.

Figa and 2b show the Zeta potential of the suspension in ethanol before and after functionalization.

Figa and 3b show the Zeta potential of the suspension in the water before and after functionalization.

A detailed description of the invention.

In the present work, unexpectedly, it was found that bifunctional compounds capable of contact with nanoparticles, formed by different types of oxides of transition metals and IU is Allami, forming stable complexes.

In these bifunctional binder additional functional group which does not react with the inorganic metal surface) leads to changes in the solubility of the nanoparticles in a liquid medium, making the nanoparticles suitable for production processes of different types of new materials (some types of hydrophilic plastics, fibers); this group also makes possible the interaction with a variety of complex substances such as biopolymers, cyclodextrins, antibodies, and drugs for use in the pharmaceutical and diagnostic field.

In addition, the use of bifunctional compounds allows to obtain complexes of nanoparticles with a binder, to achieve full and compact coating nanoparticles without significant changes defined by its properties (e.g., magnetic or optical properties).

Among other advantages, it is necessary to pay attention to the fact that due to the complete coverage of the surface, resulting from the use of these binders, the nanoparticles are non-toxic.

According to the present invention, the expression "bifunctional compounds" means thiols, carboxylic acids, hydroxamic acids, esters of phosphoric acids and their salts having an aliphatic chain, to the which has a second functional group in the terminal position (referred to as ω-position).

The second functional group is mainly selected from the group consisting of HE, NH2, COOH, COOR3where R3defined below.

More specifically, bifunctional compounds according to the present invention are compounds of the General formula:

Rl-(CH2)n-R2

in which n denotes an integer from 2 to 20,

R1selected from the group consisting of HE, NH2, COOH,

R2choose from CONHOH, PO(OH)2, PO(OH)(OR3), COOH, SH,

R3denotes an alkaline metal, mainly K, Na or Li, or protective organic group.

The above-described bifunctional compounds are known or can be obtained according to known methods.

The method of obtaining, as a rule, implies the beginning of the synthesis on the basis of a simple bifunctional compounds, commercially available (for example, carboxylic acids or ω-functionalityand alcohols), protection of functional groups in the ω-position and, finally, the activation of the carboxyl (or alcohol) function for the subsequent introduction or hydroxamic fosforescente functionality.

According to the present invention, the term "nanoparticles" means particles with sizes from 1 to 200 nm.

Particularly preferred according to the invention are nanoparticles consisting of metals and oxides of metals that belong to easy to a number of transition metals, in particular, compounds of the General formula MIIMIII2O4where MII=Co, Ni, Fe, Mn and MIII=FeIII, Co, Al; oxides of Fe2O3type maghemite; in particular ferrite cobalt CoFe2O4, magnetite FeFe2O4maghemite γ-Fe2O3; metal particles consisting of metallic Fe0and Co0and their alloys, even with noble metals.

Complexes of nanoparticles and a binder receive, by introducing the above-described mono - or bifunctional derivatives in the reaction with the above-described nanoparticles thus, to fully cover the free surface.

The cooking process by adding a dispersion of the nanoparticles in an organic solvent (e.g., ethylene glycol) in the reaction with the preferred binder with stirring for several hours at low temperature.

The product is then precipitated (e.g., acetone), centrifuged, separated and, if necessary, purified by re-dispersion in a suitable solvent and re-deposition. The degree of coverage and the degree of reaction is evaluated using different experimental methods, including Tg DSC-TG, IR-spectroscopy with Fourier transform (FT-IR), elemental analysis and method of dynamic light scattering (MDS DLS).

It was so is e determined the effect of surface functionalization on the magnetic properties of the product.

Thus obtained functionalityand nanoparticles can be used in processes that require special hydrophilic-hydrophobic behavior, in particular, in the production of plastics (such as polyethylene or polyester) or synthetic fibers (e.g. nylon) and natural fibers (e.g. cotton).

Nanoparticles treated with bifunctional binder, can be further modified by the functional group defined reactive molecules (e.g., cyclodextrins, Polevoy acid, antibodies, and drugs), proteins or polymers (for example, polyamidoamine), with the aim to connect the particle properties (magnetism) with the properties of these molecules or polymers (biocompatibility, invisible to the immune system), or these proteins.

Magnetic properties can be used to design the contrast agents of the General action or selective contrast agents, for analysis of magnetic resonance imaging or in combination with medication, education, transportation systems, the release of which is controlled by the heating of the particles due to the hyperthermic effect.

In General, it can be argued that for the Assembly of complex nanoparticle/bifunctional binder, which we will call functionalityand nanoparticle: the above molecule, a polymer or protein, may be subject to the following criteria.

a) Functionalityand nanoparticles, which contain amines as the outer (external) functional groups can be associated with these molecules, polymers or proteins, which may contain one of the following functional groups: carboxylic acids, aldehydes and acrylamide.

b) Functionalityand nanoparticles, which contain carboxylic acid as an external functional groups can be associated with biopolymers, proteins or molecules (cyclodextrins, folic acid, antibodies, and drugs), which, in turn, may contain one of the following functional groups: alcohols, amines and thiols.

c) Functionalityand nanoparticles that contain auxiliarily group as an external functional groups can be associated with biopolymers, proteins or molecules (cyclodextrins, folic acid, antibodies, and drugs), which, in turn, may contain one of the following functional groups: carboxylic acid.

As you can see, the connection formed by complexes of nanoparticles/bifunctional binder and the above-described functional molecules can be obtained by different preparative methods.

Ways

Method A.

Functionalization of nanoparticles simple bifunctional binder, such as, for example, ω-hydroxy-, ω-carboxy, ω-aminocarbonyl acid; ω-hydroxy-, ω-carboxy, ω-aminohydrocinnamic acid; ω-hydroxy-, ω-carboxy, ω-aminophosphine acid; ω-hydroxy-, ω-carboxy - ω-aminothiol. The subsequent binding biofunctionalization particles with molecules, proteins or polymers through a bifunctional binder.

Method C.

Anchoring molecules, polymers or modified proteins by binding to functionalized nanoparticles by sharing binder.

Method C.

Identical to method a except that the functionalization of the nanoparticles is carried out by mixtures biofunctionalization binder.

Method D.

Identical way except that the functionalization of the nanoparticles is carried out by mixtures biofunctionalization binder.

Method E.

Direct functionalization of nanoparticles with molecules, polymers or proteins previously associated with a suitable bifunctional binder.

Method F.

Functionalization of nanoparticles mixtures containing molecules, polymers or proteins, is already associated with a suitable bifunctional binder and any other bifunctional binder.

To better illustrate izaberete is s, below are some specific examples of the preparation of the binder, complexes and their subsequent functionalization.

Example 1.

Synthesis of 12-amino-N-hydroxybudesonide.

a) Synthesis of 12-amino(tert-butoxycarbonyl)dodecanol acid.

In a 250 ml two-neck flask firm Sovirel with a magnetic stirrer, equipped with a perforated membrane and the valve for argon, dissolved in dioxane (20 ml) selling 12-aminododecanoic acid (5.2 g, from 25.8 mmol) and added Boc2O (6.5 ml, 28 mmol). The system is brought to 0°C and slowly added dropwise 2 N. NaOH (13,2 ml). The solution is allowed the opportunity to react under the conditions of heating under reflux for 24 hours, add distilled water (60 ml) and extracted with Et2O (2×30 ml). The aqueous phase is acidified with citric acid (25 wt.%) to pH 5, extracted with EtOAc (3×50 ml), combine the fractions obtained, dehydrated using MgSO4and evaporated on the rotavapor rotary evaporator and high vacuum pump. Obtain 6.0 g of 12-amino(tert-butoxycarbonyl)dodecanol acid (yield 73%).

TPL 80-82°C.

Data spectroscopy:

IR: 3385, 2919, 2853, 1727, 1688, 1520, 1469, 1365, 1246, 1172, 946.

1H-NMR (400 MHz, CD3OD): 1,36 (s, N), 1,40-1,60 (m, N), 2,35 (t, J=7,0 Hz, 2H), 3,00 (t, J=6.6 Hz, 2H), 4,80 (with, of user., 1H).

13C-NMR (100,2 MHz, CD3OD): 24,9; 26,7; 27,7; 29,1; 29,3; 29,4 (2CH2); 29,48; 29,5; 9,8; 33,8; 40,2; 78,6; 157,3; 176,4.

Mass spectrum: 315 (M+).

b) Synthesis dicyclohexylammonium salt of 12-amino-(tert-butoxycarbonyl)dodecanol acid.

Dicyclohexylamine (3,92 ml of 19.7 mmol) are added to a suspension of 12-amino-(tert-butoxycarbonyl)dodecanol acid (5.8 g, 18.4 mmol) in methanol (20 ml). The resulting suspension is stirred 10 min at room temperature, is removed in vacuum, the solvent and gain of 9.1 g of product (yield 100%) as a powdery white solid, which is used further without any purification.

c) Synthesis of tert-butyl methyl ether (12)-(benzylamino)-12-octodecimspinosus acid.

Dicyclohexylammonium salt of 12-amino-(tert-butoxycarbonyl)dodecanol acid (9.1 g, 18.4 mmol) was placed in a 100-ml two-neck flask firm Sovirel with a magnetic stirrer, equipped with a perforated membrane and the valve for argon, and add pyridine (1.50 ml, of 15.2 mmol) and dichloromethane (18 ml).

Add using a syringe titillated (22,1 mmol, of 1.62 ml) and leave the mixture to react for 5 min at room temperature. At the same time in another two-neck flask is placed a portion of the hydrochloride benzylacrylamide (2.9 g, 18.4 mmol) and add 4-dimethylaminopyridine (DIMAP, 3.6 g, 3.0 mmol) and dichloromethane (36 ml). The resulting solution was added dropwise with a syringe into the first flask and the resulting mixture stirred the 1 hour at room temperature. The solvent is removed on the rotavapor rotary evaporator and perform purification via column chromatography on silica gel (eluent: ethyl acetate/petroleum ether, 1:1), which leads to the separation of 3.8 g (yield 50%) of product as a yellow-white solid.

TPL-73°C.

Data spectroscopy:

IR: 3346, 3298, 2922, 2851, 1682, 1657, 1540, 1356, 1269, 1254, 1171.

1H-NMR (400 MHz, CDCl3): 1,05-1,10 (m, N), of 1.40 (s, N), 1,40-of 1.55 (m, 2H), 2.00 (evens, user., 2H), 3.00 and-3,10 (m, 2H), 4,80 (with, of user., 1H), the 4.90 (s, 2H), 7,25-to 7.35 (m, 5H), 9,25 (with, of user., 1H).

13C-NMR (75,3 MHz, CDCl3): 25,2, 26,4, 28,1, 28,8, 28,9, 29,1, 29,2, 29,7, 32,7, 40,3, 77,5, 78,6, 128,0, 128,7 (2ArCH), 135,3, 155,8, 170,1.

Mass spectrum: 420 (M+).

d) Synthesis of 12-amino-N-(benzyloxy)dodecanolide.

In odnogolosy flask containing tert-butyl ether (12)-(benzylamino)-12-octodecimspinosus acid (3,14 g, 7.5 mmol), added in an inert atmosphere chloroform (30 ml). Slowly added dropwise triperoxonane acid (5.6 ml, 7.5 mmol) and stirred the mixture for 1 hour at room temperature. The solvent is removed on the rotavapor rotary evaporator and add concentrated ammonia to pH 9. Add distilled water (30 ml) and chloroform (30 ml). The extraction was performed with chloroform (3×25 ml), the organic phase is dehydrated by magnesium sulfate, filter and remove the solvent, obtaining 2.0 g (yield 85%) of product as a yellowish solid.

TPL=76-8°C.

Data spectroscopy:

IR: 3357, 3225, 2907, 2841, 1657, 1553, 1369, 1203, 1057.

1H-NMR (400 MHz, CDCl3): 1,00-1,40 (m, N), 1,45-1,55 (with, of user., 2H), 2.00 (evens, user., 2H), 2,45 (with, of user., 2H), 4.80 to 5,00 (m, user., 5H), 7,20-7,40 (m, 5H).

13C-NMR (75,3 MHz, CDCl3): 25,3, 26,5, 28,9, 29,0, 29 1, 29,2, 29,24, 32,7, 32,9, 41,5, 77,5, 128,2, 129,0 (2ArCH), 135,7, 170,7.

Mass spectrum: 320 (M+).

e) Synthesis of 12-amino-N-hydroxybudesonide.

Carry out the hydrogenation with hydrogen in a Parr reactor. The reactor is placed 120 mg Pd/C, 12-amino-N-(benzyloxy)dodecane (1.0 g, 2.4 mmol) and ethanol (40 ml). It is preferable to heat the product in ethanol at 50°C in Erlenmeyer flask. Hydrogenation lasts 30 hours, followed by filtration on a porous membrane with a layer of cellite, washing the membrane several times with ethanol. The solution is evaporated on the rotavapor rotary evaporator and high vacuum pump, getting a 12-amino-N-hydroxydecanoic in the form of a white solid (500 mg, yield 66%).

TPL wing 112-116°C.

Data spectroscopy:

IR: 3247, 2973, 2856, 1712, 1635, 1465, 1207, 1155, 1041.

1H-NMR (400 MHz, CDCl3): 1, 10-1,60 (m, N), 2,0 (t, user., 2H), 2.70 height is 2.75 (m, 4H), 6,80 (with, of user., 1H), 7,40 (with, of user., 1H).

13C-NMR (75,3 MHz, CDCl3): the interval of CH225,9-33,0, 41,8, 169,8.

Mass spectrum: 230 (M+).

According to the same synthetic Protocol of 12 hydroxydecanoic acid can be obtained N-12-dihydroxytoluene.

Example 2.

Synthesis of one-deputizing 12-aminododecanoic potassium.

a) Synthesis of tert-butyl ester 12-hydroxydesipramine acid.

In a 100-ml two-neck flask with reflux condenser and magnetic stirrer is placed under a static layer of nitrogen, was placed a portion of 12-aminododecanoic-1-ol hydrochloride (3,34 g, 14.1 mmol) and add pyridine (40 ml), 'Pr2NEt (of 2.45 ml, 14.1 mmol) and Vos2On (3,24 ml, 14.1 mmol). The mixture is stirred for 60 hours at 70°C, evaporated on the rotavapor rotary evaporator and high vacuum pump and purify the product by column chromatography on silica gel, using as eluent a mixture of petroleum ether/ethyl acetate, 1:1. Allocate 3.1 g of tert-butyl ester 12-hydroxydesipramine acid in the form of a white solid with a yield of 73%.

TPL 78°C.

Data spectroscopy:

IR: 3424, 3370, 2920, 2852, 1686, 1523, 1172, 1058.

1H-NMR (400 MHz, CDCl3): 1,20-1,30 (with, of user., 20N), 1,40 (with, of user., N), 3,15 (bis, 2H), 3,6 (t, J=8.5 Hz, 2H), 4,4 (with, of user., 1H).

13C-NMR (75,3 MHz, CDCl3): 24,8, 26,7, 27,6, 29,0, 29,2 (2CH2), 29,5, 29,6, 29,7, 29,73, 33,7, 40,1, 78,9, 157,1.

Mass spectrum: 301 (M+).

b) Synthesis of tert-butyl ester 12-bromoderivatives acid.

In a 250 ml two-neck flask with reflux condenser and magnetic stirrer is placed under a static layer of nitrogen, t is et-butyl ether 12-hydroxydesipramine acid (of 3.07 g, 10.2 mmol) dissolved in dichloromethane (75 ml) and add PPh3(2,94 g, and 11.2 mmol) and NBS (2,42 g of 10.7 mmol). The mixture is stirred at boiling for 24 hours, evaporated on the rotavapor rotary evaporator and the product purified by column chromatography on silica gel, using as eluent a mixture of petroleum ether/ethyl acetate, 3:1. Produce 2.9 g of tert-butyl ester 12-bromoderivatives acid in the form of a low-melting white solid with a yield of 78%.

TPL 42-44°C.

Data spectroscopy:

IR: 3421, 3366, 2924, 2853, 1688, 1521, 1170, 1061.

1H-NMR (400 MHz, CDCl3): 1,10-1,20 (with, of user., 20N), 1,35 (with, of user., N), 3,05 (with, of user., 2H), 3,60 (t, J=6.0 Hz, 2H), 4,80 (with, of user., 1H).

13C-NMR (100,4 MHz, CDCl3): 26,4, 27,8, 28,1, 28,4, 28,9, 29 1, 29,15, 29,2, 29,7, 32,5, 33,4, 40,2, 78,2, 155,2.

Mass spectrum: 363 (M+).

c) Synthesis of tert-butyl methyl ether (12)-(diethoxyphosphoryl)dodecylamino acid.

In a 250 ml odnogolosy flask with reflux condenser is placed a portion tert-butyl ester 12-bromoderivatives acid (2,39 g, 6.6 mmol) and added triethyl phosphate (2.25 ml of 13.1 mmol). The reaction mixture is brought to 150°C and stirred under a static layer of nitrogen. After 18 h odnogolosy flask is connected to the high-vacuum pump for removal of volatile products, and the resulting thick oil is placed directly on a silica gel chromatographic column and elute the mixture is Yu ethyl acetate/petroleum ether, 1:1, highlighting 0.4 g of tert-butyl methyl ether (12)-(diethoxyphosphoryl)dodecylamino acid (yield 14%) as a colourless oil.

Data spectroscopy:

IR: 3420, 3371, 2922, 2850, 1687, 1218, 1060.

1H-NMR (400 MHz, CDCl3): 1,20-1,45 (m+t, J=7,0 Hz, N), 1,55-1,60 (bm, 2H), 3,05 (kV OSiR., 2H), 3,90-to 4.15 (m, 4H).

13C-NMR (75,3 MHz, CDCl3): 15,6,24,9 to 29.8 (10CH2+t-Bu), 40,0, 61,2, 65,2, 78,3, 155,6.

Mass spectrum: 421 (M+).

d) one-deputizing 12-aminododecanoic potassium.

In odnogolosy flask with reflux condenser is placed a portion tert-butyl ether (12)-(diethoxyphosphoryl)dodecylamino acid (0.35 g, 8.3 mmol) and add concentrated HCl (1.5 ml). Bring temperature up to 100°C and stirred mixture under static layer of nitrogen. After 18 hours the mixture is evaporated using a high vacuum pump, receiving light brown rubbery solid.

Data spectroscopy:

IR: 3431, 2900, 2841, 1631, 1470, 1172, 1045, 952.

1H-NMR (400 MHz, CDCl3): broadened signals: (1,0-1,80 m), user., 2,80,, user., 3,40.

13C-NMR (100,4 MHz, CDCl3): 23,0-28,8 (overlapping signals), 31,2, 33,4.

Mass spectrum: 265 (M+).

Example 3

Synthesis of one-deputizing 12-gidroksimetilfurfural potassium.

a) Synthesis of 12-bromododecane.

In a 250 ml two-neck flask under a static layer of nitrogen was placed a portion of 12-bromide is anola (5.0 g, of 18.9 mmol), add pyridine (25 ml) and bring the mixture to 0°C using an external bath of ice and salt. Slowly added dropwise to the benzoyl chloride and, after the addition has been finished, remove the ice bath and stirred the mixture at room temperature. After 18 hours, add ethyl acetate (100 ml) and distilled water (100 ml). The organic phase is washed three times with distilled water (3×50 ml) and dehydrated over anhydrous sodium sulfate, and then filtered under vacuum to remove solvent on the rotavapor rotary evaporator and high vacuum pump. The product was then purified using column chromatography on silica gel, using as eluent a mixture of petroleum ether/ethyl ether, 5:1. Allocate 4.5 g 12-bromododecane in the form of a colourless oil with a yield of 65%.

Alternatively, after 18 hours the reaction mixture are added ethyl acetate (100 ml) and the mixture is then washed with saturated aqueous copper sulfate (3×80 ml) to remove pyridine. In this case, the output increases to 90% without column chromatography and the product is directly used in the subsequent stage.

Data spectroscopy:

IR: 2926, 2853, 1716, 1269, 1109.

1H NMR (400 MHz, CDCl3): 1,10-to 1.60 (m, 16 H), 1,60-1,80 (m, 4H), 3,55 (t, J=6,8 Hz, 2H), 4,25 (t, J=6,8 Hz, 2H), 7,30-7,35 (m, 3H), 8,00-with 8.05 (m, 2H) ppm

13With NMR (75,3 MHz, CDCl3): 25,8, 26,6, 28,5, 28,6-29,3 (SN2

Mass spectrum: 369 (M+).

b) Synthesis of 1,2-diethoxypropionate

In odnogolosy flask with reflux condenser is placed a portion of 1,2-bromododecane (425 g, 11.5 mmol) and add triethylphosphite (4,11 ml, 24 mmol). The reaction mixture is brought to 150°C and stirred under a static layer of nitrogen. After 24 hours odnogolosy flask is connected to the high-vacuum pump for removal of volatile products, and the resulting thick oil is placed directly on a silica gel chromatographic column and elute with a mixture of ethyl acetate/petroleum ether, 1:1, highlighting 4.0 g (yield 82%) of 1,2-diethoxypropionate in the form of a colorless oil.

Data spectroscopy:

IR: 3663, 3425, 2927, 2844, 1721, 1218, 1064.

1H-NMR (400 MHz, CDCl3): of 1.30 (t, J=7,0 Hz, 6N), of 1.40 and 1.80 (m, 22N), 3,95-of 4.05 (m, 4H), 4,25 (t, J=6.0 Hz, 2H), 7,40-the 7.65 (m, 3H), 8,00-with 8.05 (m, 2H) ppm

13C-NMR (75.3 MHz, CDCl3): 16,0, 22,6, 24,2-34,1 (10CH2), 61,0, 65,3, 128,2, 129,4, 131,4, 167,1.

Mass spectrum: 426 (M+).

c) Synthesis of one-deputizing 1,2-gidroksimetilfurfural potassium.

In odnogolosy flask with reflux condenser is placed a portion 12 of diethoxypropionate (4.0 g, 9.3 mmol) and add concentrated HCl (10 ml). Bring the mixture to a temperature of 100°C and stirred under a static layer of nitrogen. After 72 hours, add ethyl acetate (80 ml) and distilled water (40 ml). Producing the separation in a separating funnel and extracted with water three times with ethyl acetate (3×50 ml). The combined organic phases are washed with saturated NaCl solution, dried with anhydrous sodium sulfate and evaporated on the rotavapor rotary evaporator and high vacuum pump. Hold column chromatography on silica gel, using as eluent a mixture of petroleum ether/ethyl acetate, 1:1. First allocate a side formed benzoic acid and then, when replacing the eluent on pure methanol, isolated in the quality of the product 12-benzyloxycarbonylamino acid. Continuing chromatography on a column, there is also a product of complete hydrolysis - 12-hydroxycholecalciferol acid. The last two products (about 2.0 g) kept together and used in the next stage.

Two of the selected product is placed in odnogolosy flask with reflux condenser and add methanol (50 ml), distilled water (20 ml) and potassium carbonate (13 mmol, 1.8 g). The mixture is brought to 50°C. and stirred for 18 h under static layer of nitrogen. The methanol is removed on the rotavapor rotary evaporator and the residue is shaken out three times with ethyl ether (3×20 ml) to remove the formed side methylbenzoate. To the water solution was added 10%HCl until acidic pH. After precipitation of solid white matter water is removed on the rotavapor rotary evaporator and high vacuum pump. The obtained solid is dissolved in methanol and decanted, removing t is m the chloride of potassium.

TPL 270-279°C.

Data spectroscopy:

IR: 3357, 2917, 2850, 1467, 1233, 1162, 1010, 936.

1H-NMR (400 MHz, D2O): 1,10-1 90 (m, 22N), 3,40 (with, of user., 2H).

13C-NMR (75,3 MHz, D2O): 24,5, 25,3, 29,0-29,3 (SN2), 30,5, 31,7, 61,9.

Mass spectrum: 266 (M+).

Thus obtained phosphoric acid is treated with equimolar amount of KOH and heated in methanol to obtain the corresponding potassium salt. Receive (from 12-diethoxyphosphoryloxy) 1.3 g of potassium salt of 12-gidroksimetilfurfural, yield 57%, in the form of a powdery white solid.

TPL 336-348°C.

Data spectroscopy:

IR: 3308, 2918, 2851, 2364, 1651, 1553, 1399, 1082, 977, 831.

1H-NMR (400 MHz, CD3OD): 1,20-of 1.85 (m, 22N), 3,50 (t, J=6,8 Hz, 2H).

13C-NMR (75,3 MHz, CD3OD): 22,9, 25,7, 29,1-29,5 (SN2), a 30.7 (d, 1=12 Hz), 61,8.

Mass spectrum: 265 (M-), 39 (K+).

Example 4.

Synthesis of one-deputizing 13 ethoxy-13-extremelypopular potassium.

a) Synthesis of ethyl-12-hydroxydecanoate.

In a 100-ml two-neck flask with reflux condenser and magnetic stirrer in a static stream of nitrogen was placed a portion of the 12-hydroxydecanoic acid (5.0 g, 23.2 mmol), and add ethanol (20 ml) and acetylchloride (of 1.62 mmol, and 0.09 ml, 0.1 EQ.). The mixture is stirred for 24 hours at boiling, evaporated on the rotavapor rotary evaporator and high vacuum pump is e and purify the product by column chromatography on silica gel, using as eluent a mixture of petroleum ether/ethyl acetate, 5:4. Allocate 3,30 g ethyl-12-hydroxydecanoate as a pale yellow oil with a yield of 96%.

Data spectroscopy:

IR:. 3662, 2926, 2853, 1731.

1H-NMR (400 MHz, CDCl3): 1,05-1,25 (m, 17H), 1,40-1,60 (m, 4H), 2,17 (t, J=7.2 Hz, 2H), 2,34 (s, 1H), 3,49 (t, J=6,8 Hz, 2H), 4,01 (1, J=7,2 Hz, 2H).

13C-NMR (75,3 MHz, CDCl3): 14,0, 24,7, 25,6, 28,9, 29,0, 29,2, 29,2, 29,3, 29,4, 32,6, 34,2, 59,98, 62,6,173,8.

Mass spectrum: 234 (M+).

b) Synthesis of ethyl-12-bromododecane.

In a 100-ml dvuhholos flask with reflux condenser and magnetic stirrer under a static layer of nitrogen dissolved ethyl-12-hydroxydecanoate (1.65 g, 6.7 mmol) in dichloromethane (20 ml) and add PPh3(1,93 g, 7.4 mmol) and NBS (N-bromosuccinimide) (1.6 g, 7.0 mmol). The mixture is stirred at boiling for 24 hours, evaporated on the rotavapor rotary evaporator and the product purified by column chromatography on silica gel, using as eluent a mixture of petroleum ether/ethyl acetate, 5:1. Allocate 1.92 g (yield 92%) of ethyl-12-bromododecane as a pale yellowish oil.

Data spectroscopy:

IR: 2926, 2853, 1731.

1H-NMR (400 MHz, CDCl3): 1,20-of 1.45 (m, 15 NM), 1,55-1,65 (m, 4H), 1,80-1,90 (m, 2H), 2,30 (t, J=7,0 Hz, 2H), 3,40 (t, J=7,l Hz, 2H), 4,10 (1, J=7,2 Hz, 2H).

13C-NMR (75,3 MHz, CDCl3): 14,2, 24,9, 28,1, 28,7, 29,1, 29,3 (2CH2), 29,4, 32,8, 33,9, 34,3, 61,1, 173,8.

Mass spectrum: 296 (M+).

c) SinTe the ethyl ester of 13-(diethoxyphosphoryl)tridecanoic acid.

In odnogolosy flask with reflux condenser is placed a portion of the ethyl-12-bromododecane (1.8 g, 7,37 mmol) and add triethylphosphite (2.6 ml, 15 mmol). The reaction mixture is brought to 150°C and stirred under a static layer of nitrogen. After 24 hours, plug coming from the throat of the flask hose to the high-vacuum pump in order to remove volatile products, and the resulting thick oil directly chromatographic on a column of silica gel, using as eluent a mixture of ethyl acetate/petroleum ether, 1:1, and allocate 2.5 g (yield 94%) of ethyl ester of 13-(diethoxyphosphoryl)tridecanoic acid as a colourless oil.

Data spectroscopy:

IR: 3684, 3445, 2978, 2853, 1730, 1216, 1058.

1H-NMR (400 MHz, CDCl3): 1,05-1,15 (m, 25N), of 1.40 and 1.80 (m, 4H), 2,0-2,1 (m, 2H), 4.00 points (with, of user., 6N).

13C-NMR (75,3 MHz, CDCl3): 14,0, 15,9, 16,2 (d, J=5.6 Hz), 22,1, 22,2, 24,7, 26,2, 26,8, 29,0, 29,1, 29,2, 30,3 (d, J=16.1 Hz), 34,1, 59,9, 61,11 (d, J=6.4 Hz), or 63.7 (d, J=5.6 Hz), 173,6.

Mass spectrum: 364 (M+).

d) Synthesis of one-deputizing 13 ethoxy-13-extremelypopular.

In odnogolosy flask with reflux condenser is placed a portion of ethyl ether 13-(diethoxyphosphoryl)tridecanoic acid (1.3 g, 3.6 mmol) and add concentrated HCl (2 ml). The temperature of the mixture is brought to 100°C. and stirred mixture under static layer of nitrogen. After 6 days, the mixture is evaporated at high vacuum pump, the floor is th sticky white solid. Analysis1H-NMR shows still exist ester group. Add KOH (460 mg in 20 ml of a mixture water/methanol, 1:1) and again the mixture is stirred over night at room temperature. In the morning the mixture is dried and extracted with ethyl acetate possible organic impurities. The aqueous phase is evaporated, add to the resulting sticky white solid substance in 10 ml of methanol and boil the mixture under reflux for 5 minutes, the Solution is separated with a pipette and the solid white residue is dried in high vacuum and characterized by spectroscopy. Receive 800 mg (yield 62%)of the product as a powdery white solid.

TPL 350-360°C.

Data spectroscopy:

IR: 3411 (user.): 2922, 2848, 1649, 1566, 1410, 1041, 977.

1H-NMR (400 MHz, D2O): 1,00-1,40 (m, 20N), 2,0 (t, J=7,6 Hz, 2H).

13C-NMR (100,3 MHz, D2O): 23,5, 24,4, 26,1, 28,7, 28,9, 31,3, 37,87 (only distinguishable signals for CH2).

Mass spectrum (m/z): 278/2=139 (M+).

Following the same Protocol synthesis, you can get 12 hydroxylamino-12-oxododecanoyl acid.

Complexes of nanoparticles/bifunctional binder.

Example 5.

Synthesis of ethyl ether 12 hydroxylamino-12-oxododecanoyl acid.

Synthesis of ethyl-12-hydroxydecanoate.

In a two-neck flask with reflux condenser are introduced with stirring in a stream of nitrogen 12-hydroxydecanoate acid (5.0 g, 23.2 mmol), ethanol (20 mmol) and acetylchloride (0.9 ml, of 1.62 mmol) and boil the mixture for 24 hours. Then the solution is evaporated on a rotary evaporator under high vacuum, and purify the crude product using column chromatography on silica gel, using as eluent a mixture of petroleum ether/ethyl acetate, 5:4. Allot of 5.45 g (yield 96%) of the desired product as a pale yellow oil.

Data spectroscopy:

1H-NMR, δ, ppm (400 MHz, CDCl3)1 1,05-1,25 (m, 17H), 1,40-1,60 (m, 4H), 2,17 (t, 3=7.2 Hz, 2H), 2,34 (s, 1H), 3,49 (t, J=6,8 Hz, 2H), 4,01 (1, J=7,2 Hz, 2H)
13C-NMR, δ, ppm (100,6 MHz, CDCl3)14,0, 24,7, 25,6, 28,9, 29,0, 29,2, 29,3, 29,4, 32,6, 34,2, 59,98, 62,6, 173,8
IR, cm-13423, 2928, 2855, 1737
Mass spectrum245 (M+1)+

Synthesis of 12-ethoxy-12-oxododecanoyl acid.

In odnogolosy flask, equipped with a perforated membrane, to periodni acid (5,13 g of 22.5 mmol) is added in a stream of argon with stirring acetonitrile (80 ml) and after 15 min cook is the temperature to 0°C. In these circumstances, the flask was added dropwise a solution of ethyl-12-hydroxydecanoate (5; 2.5 g, 10.2 mmol) and pyridine-chlorochromate (RCA 44 mg, 0.20 mmol) in acetonitrile (20 ml). After adding the reaction of lead within 24 hours at room temperature. The reaction is stopped by the addition of ethyl acetate (100 ml). The reaction solution is washed with a solution (1:1) distilled water/brine (2×50 ml), saturated aqueous solution of sodium bisulfite (NaHSO3; 2×25 ml), brine (2×50 ml). The organic phase is dehydrated sodium sulfate and filtered under vacuum. The solvent is distilled off and the product is dried in a high vacuum, receiving of 2.45 g of a white solid. The product was then purified using column chromatography using silica gel as eluent a mixture of ethyl acetate/petroleum ether, 3:1. Obtain 2.1 g (yield 80%) of the desired product as a white solid. The reaction is carried out according Hunsen, M. Synthesis, 2005, 2487-2490.

Data spectroscopy:

1H-NMR, δ, ppm (400 MHz, CDCl3)of 1.26 (m, 15 NM), to 1.61 (m, 4H), 2,28 (t, J=7,6 Hz, 2H), 2,35 (t, J=7.4 Hz, 2H), 4,12 (q, 1-7,1 Hz, 2H)
13C-NMR, δ, ppm (100,6 MHz, CD3OD)14,5, 26,0, 30,1-30,5, 34,9, 35,0, 61,3, 175,4, 177,5
IR, cm-1 2916, 2850, 1739, 1714, 1473, 1432
Mass spectrum259 (M+1)+

Synthesis of ethyl ether 12 hydroxylamino-12-oxododecanoyl acid.

In odnogolosy flask equipped with a reflux condenser, was dissolved with stirring in a stream of argon 12 ethoxy-12-oxododecanoyl acid (13; 1.5 g, 5.8 mmol) in chloroform (20 ml). Added dropwise thionyl chloride (SOCl2; of 0.64 ml, 8,8 mmol) and conducting the reaction by boiling for 3 hours. The mixture is then cooled to room temperature and remove the solvent under high vacuum. The obtained product is dissolved in dichloromethane (20 ml), mixed at room temperature and under stirring with a solution of hydroxylamine hydrochloride (0,61 g, 8,8 mmol) in pyridine (10 ml) and left in the same conditions to react for 12 hours. All the solvent is removed in high vacuum, the remaining product is dissolved in ethyl acetate (50 ml) and washed with distilled water (3×20 ml). The organic phase is dehydrated with anhydrous sodium sulfate and filtered under vacuum. After removal of the solvent and drying under high vacuum to obtain 1.3 g (yield 82%) of product as a yellow solid.

Data spectroscopy:

1H-NMR, δ ppm (400 MHz, CD OD)of 1.27 (m, 15 NM), to 1.60 (m, 4H), 2,08 (t, J=7.4 Hz, 2H), 2,30 (t, J=7.2 Hz, 2H), 4,11 (q, J=7,1 Hz, 2H)
13C-NMR, δ ppm (100,6 MHz, CD3OD)14,5, 25,9, 26,5, 30,0-30,4, 33,1, 35,0, 61,3, 173,4, 175
IR, cm-13421, 2922, 2848, 1735, 1636, 1469, 1421
Mass spectrum274 (M+1)+

Example 6.

Complexes of nanoparticles of cobalt ferrite/12-gidroksimetilfurfuralya acid (chart product 1.2).

10 g of a dispersion in diethylene glycol containing 3 wt.% nanoparticles, for example, of cobalt ferrite with a diameter of 5 nm, is added to 0.3 g of 12-hydroxycholecalciferol acid after it is dissolved in 20 g of slightly warmed ethanol. The mixture is stirred for 2 hours at room temperature. Then precipitated with acetone sample, centrifuged and separated. The sample is re-dispersed in ethanol and again precipitated, centrifuged and separated to remove impurities. The wet sample can then be re-dispersed in the desired solvent.

Example 7.

Complexes of nanoparticles of cobalt ferrite/12-amino-N-hydroxydecanoic (chart product 1.2).

10 g of a dispersion in diethylene glycol containing 3 wt.% nanoparticles, for example, of cobalt ferrite with a diameter of 5 nm, is added to 0.21 g of 12-amino-N-hydroc is dodecanolide after it dissolved in 20 g of boiling water, the mixture is stirred for 2 hours at room temperature. The sample was then precipitated with acetone, centrifuged and separated. The sample is re-dispersed in ethanol and again precipitated, centrifuged and separated to remove impurities. The wet sample can then be re-dispersed in the desired solvent.

Complexes of inorganic nanoparticles poly-functional molecule.

Example 8.

Synthesis of functionalized compounds nanoparticles with polyamidoamine (PAA), consisting of ethylenediaminediacetic acid-bisacrylamide - chart product 1.2.1.

10 g of the aqueous dispersion containing 0.1 wt.% nanoparticles, for example, of cobalt ferrite with a diameter of 5 nm, functionalized hydroxamic 12-aminododecanoic acid, is added to 10 g of a solution containing 0.02 g of the polymer. The pH value was adjusted to 8 by adding a few drops of triethylamine. The solution is stirred for 2 days in the dark at 25°C. the resulting product is then filtered using Amicon filtration systems to remove unreacted polymer. After that, the product can be left in solution or dried for analysis with a view to its characteristics.

Example 9.

The synthesis of compounds functionalized nanoparticle/cyclodextrin.

a) Sequence of operations for direct fixation cyclogest is in to the "grafted" product (chart product 1.2.1).

10 g of a dispersion in diethylene glycol containing 0.1 wt.% nanoparticles, for example, of cobalt ferrite with a diameter of 5 nm, is added to the ethanol solution containing 0.21 g hydroxamic 12-hydroxydecanoic acid after it is dissolved in 20 g of slightly warmed ethanol. The mixture is stirred for 1 hour at 60°C. then precipitated with acetone sample, centrifuged and separated. The obtained solid is re-dispersed in ethanol and again precipitated, centrifuged and separated to remove impurities. The wet sample can then be re-dispersed in DMF (15 ml). Add dicyclohexylcarbodiimide (DCC, 2 g) and 4-dimethylaminopyridine (DMAP, 0.2 g) and cool the mixture to 0°C. α-Cyclohexanecarbonyl acid (6-deoxy-6-carboxy-α-cyclodextrin, 1 g) is suspended in DMF (25 ml). The suspension is cooled to 0°C and slowly added to the reaction mixture. Stir the mixture for 48 hours at room temperature. The solution is poured into acetone (100 ml), separate the precipitate and dried it in high vacuum. The crude product can be further purified on Sephadex CM-25.

(b) Sequence of operations for direct fixation of the cyclodextrin on the functional binder with subsequent inoculation on the cobalt ferrite (chart product 1.4).

To a solution of 6-deoxy-6-carboxy-α-dextrin (1 g, 0.87 mmol) in H2O/EtOH, 1:1 (20 ml) DOB is given in DCC (197 mg, 0.96 mmol), DMAP (12 mg, 0,087 mmol, 10% catalytic amount) and hydroxamic 12-hydroxydecanoate acid (0.2 g, 0.87 mmol). The reaction mixture was stirred 72 hours at room temperature. The crude product is purified on Sephadex CM-25, receiving 360 mg (30%) of cyclodextrin associated with hydroxamic 12-hydroxydecanoic acid.

200 mg of the obtained product was dissolved in 20 ml of 96%ethanol and added to 10 ml of the dispersion in diethylene glycol containing 0.1 wt.% nanoparticles of cobalt ferrite with a diameter of 5 nm. The mixture is stirred for 2 hours at room temperature. Then precipitated with acetone sample, centrifuged and separated. The sample is re-dispersed in ethanol and again precipitated, centrifuged and separated to remove impurities. The sample can be then re-dispersed in the desired solvent.

1. Stable complexes consisting of metal oxides, iron, cobalt or their alloys in the form of nanoparticles and bifunctional compounds, where the bifunctional compounds selected from the group consisting of: thiols, carboxylic acids, hydroxamic acids, esters of phosphoric acids or their salts having an aliphatic chain containing a second functional group in the end position ω.

2. The complexes according to claim 1, where these metal oxides in the form of nanoparticles are compounds of the formula:
MIIMIIIsub> 2O4,
where MII=Co, Ni, FeII, Zn, Mn and
MIII=FeIII, Co, Al.

3. The complexes according to claim 2, where these oxides are the oxides of Fe2O3type maghemite.

4. The complexes according to claim 3, where these oxides are selected from the group consisting of: cobalt ferrite CoFe2O4, magnetite FeFe2O4, maghemite Fe2O3.

5. The complexes according to claim 4, where the specified second functional group selected from the group consisting of: HE, NH2, COOH, COOR3where R3denotes an alkaline metal or protective organic group.

6. The complexes according to claim 5, where these bifunctional compounds have the General formula (II):
R1-(CH2)n-R2,
in which: n represents an integer from 2 to 20
R1selected from the group consisting of HE, NH2, COOH,
R2choose from: CONHOH, RHO(OH)2, RHO(OH)(OR3), COOH, SH,
R3denotes an alkaline metal or protective organic group.

7. The complexes according to claim 6, where the specified alkali metal selected from the group consisting of K, Na or Li.

8. The complexes according to claims 1-7, consisting of:
the nanoparticles of cobalt ferrite/12-gidroksimetilfurfuralya acid;
the nanoparticles of cobalt ferrite/12-amino-N-hydroxydecanoic;
nanoparticle/functionalized by polyamidoamine (PAA), formed ethylenediaminediacetic acid-bisacre what reparation.

9. The method of preparation of the complexes according to claims 1 to 8, in which the dispersion of these nanoparticles is introduced into the reaction in an organic solvent with a suitable binder, stirred the mixture for several hours at low temperature and then precipitated the product, which is then separated by centrifugation and which can be purified by re-dispersion in a suitable solvent and re-deposition.

10. Compounds consisting of complexes according to claims 1-8, with a bifunctional derivative, where the external functional group specified bifunctional derivative connected with molecules, proteins or polymers.

11. Connection of claim 10, in which these molecules are selected from: cyclodextrins, folic acid, antibodies, polyamidoamine.

12. The connection 11 consisting of compounds of cobalt ferrite/12-hydroxycholecalciferol acid and carboxymethylamino cyclodextrin.

13. The connection 11 consisting of cobalt ferrite/acid cobalt ferrite/12-amino-N-hydroxybudesonide and carboxymethylamino cyclodextrin.



 

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2 cl, 7 ex, 1 tbl, 1 dwg

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16 cl, 22 ex

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