Dendritic Polymers With Enhanced Amplification and Interior Functionality

• US 20070298006A1
• Filed: 12/21/2005
• Published: 12/27/2007
• Est. Priority Date: 04/20/2004
• Status: Active Grant

• Current Assignee: Dendritic NanoTechnologies, Inc. (Loveland Products, Inc.)
• Original Assignee: Dendritic NanoTechnologies, Inc. (Loveland Products, Inc.)
• Inventors: Huang, Baohua, Svenson, Sonke, Zhuravel, Michael, Reyna, Lori, Pulgam, Veera, Swanson, Douglas, Tomalia, Donald, Heinzelmann, Joseph, DeMattei, Cordell, Chauhan, Abhay
• Granted Patent: US 7,985,424 B2
• Time in Patent Office: Days
• US Class Current: 424/78.03
• CPC Class Codes: A01N 25/10 Macromolecular compounds
• CPC Class Codes: A61K 8/85 Polyesters
• CPC Class Codes: A61K 9/0019 Injectable compositions; Intramuscular, intravenous, arterial, subcutaneous administration; Compositions to be administered through the skin in an invasive manner non-active ingredients are additionally classified in A61K47/00
• CPC Class Codes: A61K 9/5146 obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds, e.g. polyethylene glycol, polyamines, polyanhydrides
• CPC Class Codes: A61Q 15/00 Anti-perspirants or body deodorants deodorisation of air A61L9/00
• CPC Class Codes: A61Q 17/005 Antimicrobial preparations
• CPC Class Codes: C08G 63/46 Polyesters chemically modified by esterification C08G63/20 takes precedence; by after-treatment C08G63/91
• CPC Class Codes: C08G 83/003 Dendrimers
• CPC Class Codes: H01M 4/86 Inert electrodes with catalytic activity, e.g. for fuel cells
• CPC Class Codes: H01M 8/10 Fuel cells with solid electrolytes
• CPC Class Codes: Y02E 60/50 Fuel cells
• CPC Class Codes: Y02P 70/50 Manufacturing or production processes characterised by the final manufactured product

Abstract

Dendritic polymers with enhanced amplification and interior functionality are disclosed. These dendritic polymers are made by use of fast, reactive ring-opening chemistry (or other fast reactions) combined with the use of branch cell reagents in a controlled way to rapidly and precisely build dendritic structures, generation by generation, with cleaner chemistry, often single products, lower excesses of reagents, lower levels of dilution, higher capacity method, more easily scaled to commercial dimensions, new ranges of materials, and lower cost. The dendritic compositions prepared have novel internal functionality, greater stability (e.g., thermal stability and less or no reverse Michael'"'"'s reaction), and reach encapsulation surface densities at lower generations. Unexpectedly, these reactions of polyfunctional branch cell reagents with polyfunctional cores do not create cross-linked materials. Such dendritic polymers are useful as demulsifiers for oil/water emulsions, wet strength agents in the manufacture of paper, proton scavengers, polymers, nanoscale monomers, calibration standards for electron microscopy, making size selective membranes, and agents for modifying viscosity in aqueous formulations such as paint. When these dendritic polymers have a carried material associated with their surface and/or interior, then these dendritic polymers have additional properties for carrying materials due to the unique characteristics of the dendritic polymer, such as for drug delivery, transfection, and diagnostics.

Claims

1. A dendritic polymer of Formula (I):

2. The dendritic polymer of claim 1 wherein:

N_c is an integer from 1 to 20;

q is 0 or an integer from 1 to 250;

p is an integer from 1 to 250; and

m is 0 or an integer from 1 to 250; and

one of q or m must be at least 1; and

when both q and m are greater then 1, (BR) and (EX) may occur alternately with the other moiety or sequentially with multiple groups of (BR) or (EX) occurring in succession.

3. A dendritic polymer of Formula (II):

4. The dendritic polymer of claim 1, 2 or 3 wherein (C) is a simple core.

5. The dendritic polymer of claim 4 wherein the simple core is poly(glycidyl ethers) [e.g., bis-phenol glycidyl ether, pentaerythritol tetraglycidyl ether (PETGE), tetraphenylolethane glycidyl ether (TPEGE), triphenylolmethane triglycidyl ether (TPMTGE), trimethylolpropane triglycidyl ether (TMPTGE), bis(4-glycidyloxyphenyl)methane (BGPM)], tetra(epoxypropyl)cyanurate (TEPC), tris(2,3-epoxypropyl)isocyanurate (TGIC), tris[2-(acryloyloxy)ethyl]isocyanurate, 4,4′

-methylene bis(N,N′

-diglycidyl aniline) (MBDGA), diglycidyl aniline, N,N′

-diglycidyl-4-glycidoxyaniline (DGGA), sorbitol, glycerol, neopentyl, oligoneopentyl diglycidyl ether, tert-butylglycidylether, allylglycidyl ether, pentaerythritol triglycidyl ether (PETriGE), pentaerythritol triallyl ether (PETriAE), pentaerythritol tetraazide (PETAZ), neopentyl tetrapropargyl ethers, monoalkyl neopentyl tripropargyl ethers, triazides, tetraazides, aminoethanol, ammonia, polyamines [e.g., ethylenediamine (EDA), PAMAM, hexamethylenediamine (HMDA), diethylenetriamine, methylisopropylidine, alkylene bis(2-haloethylamines), arylmethyl halides (e.g., benzylic halides), piperazine, aminoethylpiperazine, hyperbranched (e.g., polylysine, poly(ethyleneimine), poly(propyleneimine), tris-2-(aminoethylamine)], linear poly(ethyleneimine), water, hydrogen sulfide, alkylene/arylene dithiols, bis(2-piperazinylethyl)disulfide (BPEDS), cystamine, 4,4′

-dithiodibutyric acid, dimethyldithiobutyrate (DMDTB), mercaptoalkylamines, thioether alkylamines, isocyanurate, heterocycles, 1,4,7,10-tetraazacyclododecane-1,4,7-tris(acetic acid) (DO3A), 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(acetic acid) (DOTA), macrocycles (e.g., crown ethers), multicarbon cores (ethylene, butane, hexane, dodecane), polyglycidylmethacrylate, poly(functional acrylates) (e.g., trimethylolpropane triacrylate (TMPTA), diallyl amine), diethylaminodiacetate, tris(hydroxymethyl)aminomethane, phosphine, porphines (e.g., porphyrins), oxiranes, thioranes [e.g., tetrathiorane (TES)], oxetanes, aziridines, azetidines, multiazido functionalities (e.g., tetra-azido adduct derived from PETGE), siloxanes, oxazolines [e.g. poly(2-ethyl-2-oxazoline) (PEOX)], carbamates, or caprolactones.

6. The dendritic polymer of claim 5 wherein the simple core is cystamine, diamine disulfides, diazido disulfides, disulfide diacetylenes, propargyl pentaerythritol triallyl ether, propargyl pentaerythritol triglycidyl ether, pentaerythritol tetraazide, pentaerythritol tetraglycidyl ether, tetraphenylolethane glycidyl ether, triphenylolmethane triglycidyl ether, trimethylolpropane triglycidyl ether, tris(2,3-epoxypropyl)isocyanurate, trimethylolpropane triacrylate, isocyanurate, heterocycles, poly(2-ethyl-2-oxazoline), multicarbon cores (ethylene, butane, hexane, and dodecane), phosphine, or linear, branched or cyclic moieties with single or multiple functional epoxides, multifunctional alkenes, alkynes or aryls, or multi-azido functionalities.

7. The dendritic polymer of claim 1, 2 or 3 wherein (C) is a scaffolding core.

8. The dendritic polymer of claim 7 wherein the scaffolding core is a capped material, such as trimethylolpropane triacrylate, or pentaerythritol tetraglycidyl ether (PETGE) or trimethylolpropane triglycidyl ether (TMPTGE) or tetraphenylolethane glycidyl ether (TPEGE) or triphenylolmethane triglycidyl ether (TPMTGE) each capped with one or more of aminoethylpiperazine, azides, propargyl functionalities, piperazine, di-imminodiacetic acids, or epoxide surface PEHAMS, or mixtures thereof.

9. The dendritic polymer of claim 1, 2 or 3 wherein (C) is a super core.

10. The dendritic polymer of claim 9 wherein the super core is either a dendrimer that serves as the core functionality or zero valent metal particles (e.g., Au, Ag, Cu, Pd, Pt), gold nanoparticles, gold nanorods, colloids, latex particles, metal oxides, nanocrystals, quantum dots, micelles, vesicles, liposomes, buckyballs, carbon nanotubes (single and multi wall), carbon fibers, silica, or bulk metal surfaces, and where other structures are attached to or grown from the core surface.

11. The dendritic polymer of claim 9 where (C) is a super core comprising the following components wherein:

PAMAM is the core with PEHAM grown on or attached to its surface;

PEHAM is the core with PEHAM grown on or attached to its surface;

PEHAM is the core with PEHAM and PAMAM grown on or attached to its surface;

PAMAM is the core with PEHAM and PAMAM grown on or attached to its surface;

PEHAM is the core with PAMAM grown on or attached to its surface;

polylysine dendritic polymer is the core and PEHAM grown on or attached to its surface;

PPI is the core and PEHAM grown on or attached to its surface;

or polyols is the core and PEHAM grown on or attached to its surface.

12. The dendritic polymer of claim 1, 2 or 3 wherein (C) is at least one nucleophilic (Nu), one electrophilic (E), or one other (O) moiety;

or a polyvalent core bonded to at least two ordered dendritic branches;

or a core atom or molecule that may be any monovalent or monofunctional moiety or any polyvalent or polyfunctional moiety, preferably a polyfunctional moiety having 2-25000 valence bonds of functional sites available for bonding with dendritic branches.

13. The dendritic polymer of claim 12 wherein (C) is nucleophilic (Nu) and is ammonia, water, hydrogen sulfide, phosphine, poly(alkylenediamines) such as ethylenediamine, hexamethylenediamine, dodecyl diamines, polyalkylene polyamines such as diethylenetriamine, triethylenetetraamine, tetraethylenepentaamine, pentaethylenehexamine, poly(propyleneimine), linear and branched poly(ethyleneimine) and poly(amidoamines), primary amines such as methylamine, hydroxyethylamine, octadecylamine, poly(methylenediamines), macrocyclic/cryptand polyamines, poly(aminoalkylarenes), tris(aminoalkyl)amines, methylisopropylidine diethylenetriamine, alkylene bis(2-haloethylamines), arylmethyl halides (e.g., benzylic halides), hyperbranched (e.g., polylysine), poly(propyleneimine), Iris-2-(aminoethylamine), heterocyclic amines, star/comb-branched polyamines, piperazine and its derivatives (e.g., aminoalkyl piperazines), ethylene glycol, polyalkylene polyols, polyalkylene polymercaptans, thiophenols, phenols, or any of these cores as capped cores [e.g., tert-butoxycarbonyl (BOC)] where at least one N_c valence is uncapped.

14. The dendritic polymer of claim 12 wherein (C) is electrophilic (E) or is converted to an (E) with Brö

nsted/Lewis acids or alkylation/acylation agents and is cyclic ethers (e.g., epoxides), oxiranes, cyclic sulfides (e.g., epichlorosulfide), aziridines, azetidines, siloxanes, oxetanes, oxazolines, oxazines, carbamates, caprolactones, carboxyanhydrides, thiolactones, sultones, β

-lactams, α

,β

-ethylenically unsaturated carboxylic esters such as (C₂-C₁₈ alkyl)acrylate esters (e.g., methyl acrylate, ethyl acrylate), (C₂-C₁₈ alkyl)methacrylate esters, acrylonitrile, methyl itaconate, dimethyl fumarates, maleic anhydride, or amides such as acrylamide, or any of these cores as capped cores where at least one N_c valence is uncapped.

15. The dendritic polymer of claim 12 wherein (C) is an other (C) moiety and is polyfunctional initiator cores that are compounds capable of generating a polyvalent core or free-radical receptor groups (e.g., olefinics), or 1,3-dipolar cyclo-addition moieties (e.g., polyalkynes and polyazides).

16. The dendritic polymer of claim 12 wherein (C) is triacrylate, tetraacrylate, triaziridine, tetraaziridine, triazide, tetraazide, trithiorane, tetrathiorane, trioxazoline, tetraoxazoline, triepoxide, tetraepoxide, diglycidyl aniline, neopentyl alcohols, aminoalkylol, alkylenediamine, tetraarylmethane, triarylmethane, triglycidylether, tetraarylmethane, tetraglycidylether, bis(glycidoxyphenyl)alkane, tetraepisulfide, trisglycidlyisocyanurate, tris(2,3-epoxypropyl)isocyanurate, methylene bis(diglycidylaniline), or tetraepisulfide.

17. The dendritic polymer of claim 12 wherein (C) is cystamine, isocyanurate, heterocycles, multicarbon cores (e.g., ethylene, butane, hexane, dodecane), phosphine, or linear, branched or cyclic moieties with single or multiple functional epoxides.

18. The dendritic polymer of claim 1 or 2 wherein (FF) is any moiety that enables a dendron to be used as a core, enables the joining of two or more dendrons together, or enables reaction with a (C), (BR), or (EX) and (BR).

19. The dendritic polymer of claim 18 wherein (FF) is hydrogen, thiols, amines, carboxylic acids, esters, ethers, cyclic ethers (e.g., crown ethers, cryptands), porphyrins, hydroxyl, maleimides, alkyls, alkenyls, alkynyls, alkyl halides, arylalkyl halides, phosphinos, phosphines, boranes, alcohols, aldehydes, acrylates, cyclic anhydrides, aziridines, pyridines, nitriles, itaconates, cyclic thiolactones, thioranes, azetidines, cyclic lactones, macrocyclics [e.g., 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(acetic acid) (DOTA), 1,4,7,10-tetraazacyclododecane-1,4,7-tris(acetic acid) (DO3A)], chelating ligands [e.g., diethylenetriaminepentaacetic acid (DTPA)] isocyanates, isothiocyanates, oligonucleotides, amino acids, peptides, cyclopeptides, proteins, antibodies or fragments, aptamers, imidazoles, azides, mercaptoamines, silanes, oxazolines, oxirane, oxetane, oxazines, imines, tosylates, metals, biotin, streptavidin, avidin, protecting groups (e.g., tert-butoxycarbonyl (BOC) or ketone solvent protected), siloxanes or its derivatives, or substituted derivatives or combinations thereof, or groups suitable for click chemistry (e.g., polyazido or polyalkyne functionality).

20. The dendritic polymer of claim 18 wherein (FF) is mercapto, amino, carboxy and carboxy esters, oxazoline, isothiocyanates, isocyanates, hydroxyl, epoxy, orthoester, acrylates, methacrylates, styrenyl, or vinylbenzylic moieties.

21. The dendritic polymer of claim 1, 2 or 3 wherein (BR) is any nucleophilic (Nu), electrophilic (E) or other (O) reagent, or may be formed from a precursor of a (BR) in situ, which (BR) is capable of reacting with (C), an extender (EX), with another branch cell or branch cell reagent (BR), or terminal functional group (TF), which results in a multiplicity or amplification of reactive groups present for the next generation G of the dendritic polymer of Formula (I), and when (BR) occurs in more than one generation, it may be the same or different (BR) moiety.

22. The dendritic polymer of claim 21 wherein (BR) is used with a co-reactant to form a core adduct and then further reacted with a second co-reactant.

23. The dendritic polymer of claim 21 wherein (BR) is an uncapped or partially capped either branched or linear, or primary or secondary polyamine, diethylenetriamine (DETA), 2-imidazolidyl-1-aminoethane (IMAE), diethanolamine (DEA), dibenzylamine (DBA), triethylenetetraamine (TETA), tetraethylenepentaamine, poly(ethyleneimine), methylamine, bis(allyl)amine (BAA), hydroxyethylamine, octadecylamine, diethyliminodiacetate (DEIDA), poly(methylenediamines) such as hexamethylenediamine (HMDA), polyaminoalkylarenes, tris(aminoalkyl)amines such as tris(aminoethyl)amine (TREN), tris(hydroxymethyl)aminomethane (TRIS), linear and branched poly(ethyleneimines), linear and branched poly(amidoamines), heterocyclic amines such as imidazolines, piperidines (PIPZ), aminoalkyl piperazines, methyl isobutyl protected 1-(2-aminoethyl)piperazine (PEA), pentaerythritol tetraglycidyl ether (PETGE);

or various other amines such as hydroxyethylaminoethylamine, (2-hydroxyethyl)ethylenediamine (HEDA), mercaptoalkylamines, mercaptoethylamine, iminodialkynes, iminodialkenes, substituted piperazine, amino derivatives of polyvinylbenzyl chloride and other benzylic amines such as tris(1,3,5-aminomethyl)benzene;

or polyols such as pentaerythritol, ethylene glycol, polyalkylene polyols such as polyethylene glycol, polypropylene glycol, 1,2-dimercaptoethane or polyalkylene polymercaptans;

thiophenols or phenols;

or acetylenic polyepoxides, hydroxyalkyl azides, alkyl azides, tri- and tetra-aziridines, tri- and tetra-oxazolines, triazoles, thiol alkyls, thiol (FF) dendrons, allyl groups, acrylates, methacrylates, or olefinic functionality or capped moieties of any of the above.

24. The dendritic polymer of claim 21 wherein (BR) is triacrylate, tetraacrylates, triepoxide, tetraepoxide, diallyl amine, diethanol amine, diethyliminodiacetate, bis(2-haloalkyl)amine, tris(hydroxymethylamine), protected diethylenetriamine (DETA), or methyl acrylate may be used, including in situ.

25. The dendritic polymer of claim 21 wherein (BR) is one or more of cyclic ethers (epoxides), oxiranes, sulfides (epichlorosulfide), aziridines, azetidines, siloxanes, oxetanes, oxazolines, oxazines, carbamates, caprolactones, carboxyanhydrides, thiolactones, P-lactams, or derivatives thereof.

26. The dendritic polymer of claim 21 wherein the (BR) is triacrylate, tetraacrylates, triepoxide, tetraepoxide, triazides, tetraazides, diallyl amine (BAA), diethanol amine (DEA), diethyliminodiacetate (DEIDA), tris(hydroxymethylamine), pentaerythritol tetraglycidyl ether (PETGE), pentaerythritol triglycidyl ether (PETriGE), pentaerythritol triallyl ether (PETriAE), (2-hydroxyethyl)ethylenediamine (HEDA), methyl isobutyl protected 1-(2-aminoethyl)piperazine (PEA), tris(2-aminoethyl)amine (TREN), tris(hydroxymethyl)aminomethane (TRIS), dimethyliminodiacetate, protected diethylenetriamine (DETA) (with ketonic solvents), or methyl acrylate, including in situ.

27. The dendritic polymer of claim 1 or 2 wherein (IF) is any active moiety formed from a ring-opening reaction resulting in interior reactive sites.

28. The dendritic polymer of claim 27 wherein (IF) is hydroxyl, thiol, amine, phosphine, alkylsilane, silane, boranes, carboxy, carboxy ester, chloro, bromo, alkene, alkyne, or alkyl- or aryl-amide.

29. The dendritic polymer of claim 27 wherein (IF) is hydroxyl, thiol, an alkylene ester or amine.

30. The dendritic polymer of claim 1 or 2 wherein (EX) is a moiety capable of lengthening the distance in the interior of the dendrimer before the growth of the next G, may occur in the dendritic polymer before or after the (BR) moiety or both before and after a (BR) and such second (EX) may be the same or different from the first (EX), may have an (IF) moiety present, and must have at least two reactive sites.

31. The dendritic polymer of claim 30 wherein (EX) is amino acids such as lysine, poly(amino acids) such as polylysine, oligoethyleneglycols, diethylenetetraamine and higher amine analogs, oligoalkylenamines protected as 5-membered imidazolidyl derivatives, fatty acids with di- or greater heterogeneous or homogenous functionality, unsaturated aliphatic and aromatic difunctional or polyfunctional moieties, ethanolamine (EA), morpholine, dicarboxylic acids, ethyl-N-piperazinecarboxylate (EPC), 2-imidazolidyl-1-aminoethane (IMAE), aryl dimercaptans, dimercaptoalkanes, triazoles, dimethylitaconate (DMI), diazides, diacetylenes, pyrrolidone, pyrrolidone esters, aminoalkyl imidazolines, imidazolidines, poly(alkyleneimidazolidines), mercaptoalkylamines, hydroxyalkylamines or heterogeneous unsaturated aliphatic and aromatic difunctional or polyfunctional moieties.

32. The dendritic polymer of claim 30 wherein (EX) is diaminoalkanes, diphenols, dithiophenols, aromatic poly(carboxylic acids), mercaptoamines, mercaptoethanol, allylamines, methyl isobutyl protected 1-(2-aminoethyl)piperazine (PEA), piperazine (PIPZ), polypiperazines, amino ethyl piperazine (AEP), ethyl-N-piperazine carboxylate (EPC), cyclic pyrrolidine derivatives, ethylenediamine (EDA), diethyliminodiacetate (DEIDA), or hyperbranched dendritic polymers such as polylysine, poly(esteramide), poly(amidoamine), poly(ethyleneimine) or poly(propyleneimine) moieties.

33. The dendritic polymer of claim 30 wherein (EX) is methyl isobutyl protected 1-(2-aminoethyl)piperazine (PEA), dimethylitaconate (DMI), methyl acrylate, ethyl-N-piperazinecarboxylate (EPC), 1,2,3-triazoles, 2-imidazolidyl-1-aminoethane (IMAE), piperazine, aminoalkyl piperazines, poly(alkylenepiperazines), methylisopropyliminoethylpiperazine (MIPIEP), diamines possessing disulfide moieties, bis(piperazinoalkyl)disulfides, or piperazine derivatives.

34. The dendritic polymer of claim 1, 2 or 3 wherein (TF) is any functionally active moiety or suitable for 1,3-dipolar addition reactions that is sufficiently reactive to undergo addition or substitution reactions, or ring-opening, polymer initiation group, or any functionally active moiety that can be used to propagate the dendritic branch to the next generation G, wherein some but not all (TF) moieties may react to form the next generation G dendrimer, the (TF) groups may be the same or different, and when the (TF) moiety is the last G, then the (TF) may be unreactive.

35. The dendritic polymer of claim 34 wherein (TF) is amino groups, [including primary and secondary amino groups, which may be capped but has at least one uncapped amino group present, (e.g., methylamino, ethylamino, hydroxyethylamino, hydrazino groups, benzylamino, glucosamine, an amino acid, mercaptoethylamino), tertiary amino, (e.g., dimethylamino, diethylamino, bis(hydroxyethyl)amino), quaternary amino groups, trialkyl ammonium, bis(hydroxyethyl)amino, bis(2-haloethyl)amino, N-alkylated, N-arylated, N-acylated derivatives];

hydroxy, mercpato, carboxy, alkenyl, allyl, aryl, methalkyl, vinyl, amido, halo, urea, oxiranyl, aziridinyl, oxazolinyl, azalactone, lactam, lactone, imidazolinyl, sulfonato, phosphonato, boronato, organosilanes, isocyanato, isothiocyanato, α

-haloacyl groups, or hydroxy alkylazido.

36. The dendritic polymer of claim 34 wherein (TF) or (M) is polyethyleneglycol, pyrrolidone, pyrrolidone esters, carboxypiperidines, piperidines, piperazines, substituted piperazines, aminoalkyl piperazines, hexylamides, aldehydes, azides, oxetanes, dyes [e.g., near infrared fluorchromes (e.g, cyanine derivatives, FITC), colorimetric (e.g., Nile red)], tris(hydroxymethyl)amidomethane, photochromic moieties (e.g., sydnones, porphines), amidoethylethanolamine, carbomethoxypyrrolidinone, succinamic acid, amidoethanol, amino acids, protected amino acids, antibodies and fragments, proteins, peptides, cyclopeptides, cationic steroids, macrocyclic groups, azacrown ethers, antibiotics/antibacterials [e.g., aminoglycosides, amphenicols, ansamycins, β

-lactams (such as penicillin, cephalosporins, cephamycins, oxacephems, carbapenems), tetracyclines, macrolides, lincosamides, 2,4-diaminopyrimidines, nitrofurans, quinolones, sulfonamides, sulfones], antineoplastics [e.g., alkyl sulfonates, aziridines, epoxides, ethylenimines and methylmelamines, nitrogen mustards, nitroureas, purine analogs, androgens, antiadrenals, antiandrogens, antiestrogens, estrogens, LH-RH analogs, progestogens, and others], folic acid and analogs, epoxides, acrylates, methacrylates, amines, carboxylates, cationic, anionic, neutral, aromatic, glucosamine or other amino sugars, biotin, avidin, streptavidin, growth factors, hormones, aptamers, 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(acetic acid) (DOTA), diethylene-triaminepentaacetic acid (DTPA), metal chelates, naphthyl sulfonates, alkyl sulfonates, aryl sulfonates, targeting groups (e.g., CD19, CD22, aptamers), hyaluronic acid, polyoxometalates, organic chromophores, polyvalent attached compounds, carbon nanotubes, fullerenes, nanocomposites, all metal nanoparticles, all semiconductor nanoparticles with all varieties of cores and shells, radioactive materials and their chelated analogues, fluorescent molecules (metal salts, organic compounds), electrically conductive molecules, light or electromagnetic energy absorbing or emitting molecules (e.g., UV, VIS (visible), IR, and microwave), radioactive analogues of drugs or diagnostic agents, silanes, siloxanes, silsesquioxane, poly(aryl-alkyl)poly(iodides), quantum dots, nanocrystals (e.g., Au, Ag, Cu, etc.), polyfluorinated molecules, surfactants, dendrons, differentiated dendrons, dendrimers, methoxy ethoxy ethoxy, polyimides (e.g., maleimide), herbicides (e.g., trifluralin, 2-phosphonomethylamino acetic acid), polyazo compounds, polyphosphazine, polyfluorinated sulfonates, heteroatoms chains and branches, lipids, starches, simple sugars (e.g., mannose, dextrose), oligonucleotides, complex sugars, drugs, such as anti-cancer agents (e.g., doxorubicin, methotrexate, and others), acetylsalicylic acid, salicylic acid, vitamins (e.g. vitamin E and C), cofactors (e.g. NADH), or antioxidants.

37. The dendritic polymer of claim 1, 2 or 3 wherein (TF) and/or (IF) can be associated with any carried material (M) which may be from one (M) to:

for (TF) the maximum possible number of z present on the surface, or for (IF) the maximum void volume and q for (IF) present in the interior.

38. The dendritic polymer of claim 34 where some or all of (TF) can be further reacted with (BR) or (EX) to further grow the dendrimer or dendron surface.

39. The dendritic polymer of claim 34 wherein (TF) is piperazine and its derivatives, alkyl piperazine, aminoalkyl piperazine, 1,2,3-triazoles, 2-imidazolidyl-1-aminoethane (IMAE), acrylate, methacrylate, acrylamides, hydroxyl, epoxide, oxazoline, alkyleneimines, lactones, azalactone, polyethylene oxides, amino ethyl imines, carboxylates, alkyl, aziridine, azides, ethyl imines, alkyl esters, epoxides, alcohols, alkylthiols, thiols, thioranes, morpholines, amines, hydrazinyl, carboxyl, allyl, azidyl, alkenyl, alkynyl, hydroxylalkylamino, protected diethylenetriamine (DETA), carboxyalkyl, pyrrolidone (and its esters), or succimidyl esters.

40. The dendritic polymer of claim 1 or 2 wherein (FF) is further reacted to provide:

amides;

esters;

alkyl-, alkenyl-, alkynyl- or aryl-ethers, optionally substituted with one or more halogens;

cyclic ethers (e.g., azacrown ethers, cryptands);

porphyrins;

thioether;

thioester;

disulfide;

maleimides;

phosphines;

phosphines;

boranes;

carboxylic acids and esters and salts;

hydrazides;

alcohols;

aldehydes;

acrylates;

cyclic anhydrides;

aziridines;

pyridines;

nitriles;

alkynes;

imidazoles;

azides;

mercaptoamines;

silanes;

oxazolines;

oxirane;

oxetane;

oxazines;

imines;

tosylates;

pyrrolidone;

cyclic thiolactones;

thioranes;

azetidines;

lactones;

azalactones;

macrocyclics [e.g., 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetra(acetic acid) (DOTA), 1,4,7,10-tetraazacyclododecane-1,4,7-tris(acetic acid) (DO3A)];

chelating ligands [e.g., diethylenetriaminepentaacetic acid (DTPA)];

isocyanates;

isothiocyanates;

oligonucleotides;

aptamers;

amino acids;

proteins, peptides, cyclopeptides, antibodies and antibody fragments;

nucleotides;

nucleosides;

metals;

biotin;

streptavidin;

avidin;

capping groups (e.g., tert-butoxycarbonyl (BOC) or solvent capped);

siloxanes or derivatives;

substituted derivatives or combinations thereof of the above;

or groups suitable for click chemistry (e.g., polyazido or polyalkyne functionality).

41. The dendritic polymer of claim 1 or 2 wherein the dendritic polymer has the physical shape, as determined by CPK models, electron microscopy, or solution characterization, of a sphere, rod, random hyperbranched, dendrigraft or core-shell(tecto)dendrimer or dendron.

42. The dendritic polymer of claim 1 or 2 wherein (TF) provides a positive overall charge to the surface.

43. The dendritic polymer of claim 42 wherein N_c=4, (TF)=piperazine, and G=1.

44. The dendritic polymer of claim 42 wherein (BR)=tris(2-aminoethyl)amine (TREN), N_c=4, and G=2.

45. The dendritic polymer of claim 1 or 2 wherein:

(C) is pentaerythritol triglycidyl ether (PETriGE), pentaerythritol tetraazide (PETAZ), tetraphenylolethane glycidyl ether (TPEGE), or triphenylolmethane triglycidyl ether (TPMTGE);

or

(BR) is 3,3-iminodiacetonitrile (IDAN), imino bis(methylphosphonic acid) (IMPA), bis(allyl)amine (BAA), diethylenetriamine (DETA), methyl isobutyl protected 1-(2-aminoethyl)piperazine (PEA), tris(2-aminoethyl)amine (TREN), N-(2-hydroxyethyl)ethylenediamine (AEEA), or 2-methyl-2-imidazoline (MIA);

or

(TF) is tetramethylsilane (TMS);

or

(EX) is triazole.

46. The dendritic polymer of claim 1 or 2 wherein (EX)=piperazine (PIPZ) or its derivatives, or triazole or its derivatives and G=0, 1, 2, 3 or 4.

47. The dendritic polymer of claim 1, 2 or 46 wherein when N_c=3 or 4, then (BR)=diethyliminodiacetate (DEIDA), bis(allyl)amine (BAA), diethanolamine (DEA), diethylenetriamine (DETA), methyl isobutyl protected 1-(2-aminoethyl)piperazine (PEA), N-(2-hydroxyethyl)ethylenediamine (AEEA), tris(hydroxymethyl)aminomethane (IRIS) or tris(2-aminoethyl)amine (TREN).

48. The dendritic polymer of claim 1, 2 or 46 wherein the core is an aliphatic moiety where (C)=pentaerythritol tetraglycidyl ether (PETGE), pentaerythritol triglycidyl ether (PETriGE), pentaerythritol triallyl ether (PETriAE), trimethylolpropane triglycidyl ether (TMPTGE), pentaerythritol tetrazide (PETAZ), tetra(epoxypropyl)cyanurate (TEPC), or tris(2,3-epoxypropyl)isocyanurate (TGIC).

49. The dendritic polymer of claim 1, 2 or 46 wherein the core is an aromatic moiety where (C)=tetraphenylolethane glycidyl ether (TPEGE) or triphenylolmethane triglycidyl ether (TPMTGE).

50. The dendritic polymer of claim 1 wherein the polymer is any one of the following:

[(C)=EDA;

(FF)=H;

(BR)=trimethylolpropane triacrylate (TMPTA);

(EX)=HSEt;

(TF)=OH;

G=1];

[(C)=HMDA;

(BR)=trimethylolpropane triacrylate (TMPTA);

(EX)=EA;

(TF)=OH;

G=1];

[(C)=HMDA;

(BR)=trimethylolpropane triacrylate (TMPTA);

(EX)=Morpholine;

(TF)=cyclic ether;

G=1];

[(C)=EDA;

(FF)=H;

(IF)=OH;

(BR)=trimethylolpropane triglycidyl ether (TMPTGE);

(TF)=Epoxy;

G=1]; and

[(C)=HMDA;

(IF)=OH;

(BR)=trimethylolpropane triglycidyl ether (TMPTGE);

(TF)=Epoxy;

G=1].

51. The dendritic polymer of claim 1 wherein the polymer is any one of the following:

[(C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF)=OH;

(BR)=pentaerythritol tetraglycidyl ether (PETGE);

(EX)=piperazine (PIPZ);

(TF)=NH;

G=0.5, 1.5, 2.5 or 3.5];

[(C)=trimethylolpropane triglycidyl ether (TMPTGE);

(FF)=Et;

(IF)=OH;

(BR)=trimethylolpropane triglycidyl ether (TMPTGE);

(EX)=piperazine (PIPZ);

(TF)=NH;

G=1.5];

[(C)=triphenylolmethane triglycidyl ether (TPMTGE);

(FF)=Et;

(IF)=OH;

(BR)=tris(hydroxymethyl)aminomethane (TRIS);

(TF)=OH;

G=1];

[(C)=trimethylolpropane triacrylate (TMPTA);

(FF)=Et;

(BR)=trimethylolpropane triacrylate (TMPTA);

(EX)=piperazine (PIPZ);

(TF)=NH;

G=1.5]; and

[(C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF)=OH;

(BR)=bis(allyl)amine (BAA);

(TF)=Allyl;

G=1].

52. The dendritic polymer of claim 1 wherein the polymer is any one of the following:

[(C)=trimethylolpropane triglycidyl ether (TMPTGE);

(FF)=Et;

(IF)=OH;

(BR)=tris(hydroxymethyl)aminomethane (TRIS);

(TF)=OH;

G=1];

[(C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF)=OH;

(BR)=tris(hydroxymethyl)aminomethane (TRIS);

(TF)=OH;

G=1];

[(C)=trimethylolpropane triglycidyl ether (TMPTGE);

(FF)=Et;

(IF)=OH;

(BR)=diethanolamine (DEA);

(TF)=OH;

G=1];

[(C)=trimethylolpropane triglycidyl ether (TMPTGE);

(FF)=Et;

(IF)=OH;

(BR)=diethyliminodiacetate (DEIDA) &

tris(2-aminoethyl)amine (TREN);

(TF)=NH₂;

G=2];

[(C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF)-OH;

(BR)=diethyliminodiacetate (DEIDA) &

tris(2-aminoethyl)amine (TREN);

(EX)=dimethylitaconate (DMI);

(TF)=CO₂Me;

G=2.5];

[(C)=tetraphenylolethane glycidyl ether (TPEGE);

(IF)=OH;

(BR)=diethylenetriamine (DETA);

(TF)=NH₂;

G=1];

[(C)=trimethylolpropane triglycidyl ether (TMPTGE);

(FF)=Et;

(IF)=OH;

(BR)=dimethylitaconate (DMI) &

tris(2-aminoethyl)amine (TREN);

(EX)=dimethylitaconate (DMI);

(TF)=CO₂Me;

G=2.5];

[(C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF)=OH;

(BR)=diethyliminodiacetate (DEIDA) &

tris(2-aminoethyl)amine (TREN);

(TF)-NH₂;

G=2];

[(C)=trimethylolpropane triglycidyl ether (TMPTGE);

(FF)=H;

(IF)=OH;

(BR)=tris(hydroxymethyl)aminomethane (TRIS);

(TF)=OH;

G=1];

[(C)=tetraphenylolethane glycidyl ether (TPEGE);

(IF)=OH;

(BR)=tris(2-aminoethyl)amine (TREN) &

tris(hydroxymethyl)aminomethane (TRIS);

(EX)=MeAcryl;

(TF)=OH;

G=3];

[(C)=tetraphenylolethane glycidyl ether (TPEGE);

(IF)=OH;

(BR)=tris(2-aminoethyl)amine (TREN);

(EX)=MeAcryl;

(TF)=CO₂Me;

G=2.5];

[(C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF)=OH;

(BR)=pentaerythritol tetraglycidyl ether (PETGE);

(EX)=piperazine (PIPZ);

(TF)=NH;

G=1.5];

[(C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF)=OH;

(BR)=pentaerythritol tetraglycidyl ether (PETGE) &

Gly;

(EX)=piperazine (PIPZ);

(TF)=OH;

G=2];

[(C)=BPEDS;

(IF)=OH;

(BR)=pentaerythritol tetraglycidyl ether (PETGE);

(EX)=methyl isobutyl protected 1-(2-aminoethyl)piperazine (PEA);

(TF)=Epoxy;

G=1];

[(C)=BPEDS;

(FF)=SH;

(IF)=OH;

(BR)=pentaerythritol tetraglycidyl ether (PETGE);

(EX)=methyl isobutyl protected 1-(2-aminoethyl)piperazine (PEA);

(TF)=NH₂;

G=1];

[(C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF)=OH;

(BR)=methyl isobutyl protected 1-(2-aminoethyl)piperazine (PEA);

(TF)=NH₂;

G=1];

[(C)=tetraphenylolethane glycidyl ether (TPEGE);

(IF)=OH;

(BR)=tris(2-aminoethyl)amine (TREN);

(TF)=NH₂;

G=1];

[(C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF)=OH;

(BR)=diethyliminodiacetate (DEIDA);

(TF)=CO₂Et;

G=1.5];

[(C)=trimethylolpropane triglycidyl ether (TMPTGE);

(FF)=Et;

(IF)=OH;

(BR)=diethyliminodiacetate (DEIDA);

(TF)=CO₂Et;

G=1.5];

[(C)=triphenylolmethane triglycidyl ether (TPMTGE);

(FF)=H;

(IF)=OH;

(BR)=diethanolamine (DEA);

(TF)=OH;

G=1];

[(C)=triphenylolmethane triglycidyl ether (TPMTGE);

(FF)=H;

(IF)=OH;

(BR)=diethyliminodiacetate (DEIDA);

(TF)=CO₂Et;

G=1.5]; and

[(C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF)=OH;

(EX)=ethyl-N-piperazinecarboxylate (EPC);

(TF)=NH;

G=0].

53. The dendritic polymer of claim 1 or 2 wherein the polymer has enhanced thermal stability, improved chemical stability, and/or a narrow polydispersity range.

54. The dendritic polymer of claim 1, 2 or 3 wherein a carried material (M) is associated with the dendritic polymer on either its interior or surface or both.

55. The dendritic polymer of claim 54 wherein the carried material (M) is associated with the interior (IF) moiety of the dendritic polymer.

56. The dendritic polymer of claim 54 wherein the carried material is a pharmaceutically active agent or pro-drug.

57. A formulation which comprises a dendritic polymer of claim 56 having at least one pharmaceutically-acceptable diluent or carrier present.

58. The dendritic polymer of claim 54 wherein the carried material is an agriculturally active agent.

59. A formulation which comprises a dendritic polymer of claim 58 having at least one agriculturally-acceptable diluent or carrier present.

60. The dendritic polymer of claim 1, 2 or 3 wherein (FF) has x=N_c−

1 and a dendron is formed.

61. A dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use as an energy and electronics applications, such as in fuel cells (e.g., membranes, catalysts), energy storage (e.g., hydrogen), microwave absorbers, infrared absorbers, solid state lighting, thermal management for devices, light emitting diodes, displays, electronic inks, interlayer dielectric, photoresist and nanoresist patterning, nanolithography, transistors, molecular electronics, telecom devices (e.g., waveguides), photonics, optical-electric converter, photographic materials, quantum dots, and stealth enhancement of materials.

62. A dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use as toner compositions either with solvent or dry formulations.

63. A dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use with dyes (such as anionic dyes, photochromic dyes, thermochromic dyes, liquid crystal), salts, antistatics, surfactants, antioxidants, solvents (such as water) or neat;

and with other desired components to yield a precipitate free ink that can be deposited on paper or another printing surface;

to coat or permeate synthetic and natural fibers useful in many applications for cloth, patterns in cloth, carpets, and other such items.

64. A dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use as a coating, caulking and filler formulations such as for paper, latex, pigments, polymers, fiberoptics, glass, metal surfaces, fiberglass, ceramics, rubber, wood, concrete, stone, fibers, and cloth.

65. A dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use as a coating for containers, stents, medical devices, catheters, implants, microarray slides, cell culture plates, electrodes and sensors.

66. A dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use as supports for use in separations or filtrations or in size calibrations.

67. A dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use as compositions for dental composites, photocurable materials, rheological modifiers, polymer adhesion agents, polymer additives, electromagnetic radiation absorbers, anticounterfeiting media, porosity modifiers, disinfectants, antibacterials, flavorings, deodorants, anti-amyloidogenic agents, to increase performance, reduce shrinkage, and/or improve adhesion.

68. A dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use as manufacturing computer memory systems, magnetic storage systems, and electronic and photonic transistors.

69. A dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use as carriers for metal ions, metal particles, magnetic and paramagnetic particles, alloys, catalysts, reuseable catalysts, metal cell foams, nanoreactors, semiconductor particles, and quantum dots.

70. A dendritic polymer of Formula (I) as claimed in any one of claims 54-57 and 60 for use as a carrier for a prodrug, drug (e.g., small organic drug, polymer drug, biomacromolecular drug, antirestinosis agent, cardiovascular agent, angiostatin, statin, antibacterial agent, antiviral agent, microbicide, amino acid, peptide, protein, oligonucleotides, nucleotides), vaccines, diagnostic agent, imaging agent, biomarker agent, oncology agent, ocular agent, nonsteriodal anti-inflammatory agent, antigen, vitamin, α

-hydroxy acid, detoxification agent, and immunosuppressant agent.

71. A dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use as a biomarker, a molecular probe, a transfection reagent, or an environmental assay reagent in in vitro, ex vivo, or in vivo applications.

72. A dendritic polymer of Formula (I) as claimed in any one of claims 1-57 and 60 for use as personal care, cosmetic or neutraceutical carrier or additive.

73. A method of treating a disease in an animal which comprises administering to the animal an effective amount of a dendritic polymer of Formula (I) as claimed in any one of claims 1-57 and 60 or the pharmaceutically-acceptable salts thereof.

74. A method of coating a solid substrate with a solution containing a dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 which comprises dipping, spraying, spin-coating, wiping, or otherwise applying the solution of the dendritic polymer to the outer surface and exposed inner surface of the substrate, removing the substrate from contact with the solution, and allowing the excess solution to evaporate in air or heat dried.

75. The method of claim 74 wherein the solution contains a mixture of solvents, surfactant, emulsifier, and/or detergent to aid the coating process, and the weight of dendritic polymer in the solution is from about 0.0001% by weight to about 50% by weight.

76. A method of transfecting eukaryotic cells by electroporation or applying to the surface of the cells a solution comprising (a) a dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 where (TF) is sufficient to have a cationic dendritic surface at a concentration of about 1 picogram to 100 mg/mL and (b) the desired oligonucleotides or polynucleic acids, and exposing the cells to the solution for a sufficient time to allow transfection.

77. A method of delivering genetic material to eukaryotic cells of plants and animals with a gene gun comprising (a) a dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 where (TF) is sufficient to have a cationic dendritic surface and conjugating a Au, Ag, Cu, Mg, or Ca particle, gold sols, gold atoms, gold containing complexes or molecules, and clusters or mixtures thereof to form a polymer-metal conjugate, wherein the maximum dimension of the conjugate is from about 1 nm to about 1000 nm as (M) or (C) and (b) the desired genetic material, oligonucleotides or polynucleic acids, which forms a gene transfection particle;

and accelerating the gene transfection particle toward a plant or animal cell with sufficient motive force to cause the gene transfection particle to penetrate and enter the cell.

78. A method of drug delivery, including therapeutic and/or diagnostic agents as drugs, to an animal using a dendritic polymer of Formula (I) as claimed in any one of claims 1-60 which comprises administering to an animal in need of such treatment, an effective amount of the drug in a pharmaceutically-acceptable excipient, carrier or diluent.

79. The method of claim 78 wherein the effective amount of drug is that known for that drug and the dose administered is the same as previously known or less to obtain the same effect from the drug.

80. The method of claim 78 wherein the drug and dendritic polymer are administered by an oral route, ampoule, intravenous injection, intramuscular injection, transdermal application, intranasal application, intraperitoneal administration, subcutaneous injection, ocular application, as wipes, sprays, gauze or other means for use at a surgical incision, near scar formation sites, or site of a tumor growth or removal or near or within a tumor.

81. A method of rheological modification of a polymer which comprises admixing the polymer, either neat or in a solvent, with a dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 in a polymer melt or solvent to modify the rheological properties of the first polymer in either the molten, solid, dissolved or dry phase by known methods and wherein (M) if present is a flame retardant, dye, UV absorber, antimicrobial agent, polymeric initiator, antistatic agent and/or antioxidant, and wherein the solution or dry mixture has a weight of dendritic polymer from about 0.0001% by weight to about 50% by weight.

82. A method of treating the skin, hair, and/or nails of an animal for cosmetic applications which comprises admixing a dendritic polymer of Formula (I) as claimed in any one of claims 1-57 and 60 in a cosmetic formulation by known methods for use as a lotion, cream, toner, powder or solvent, and then brushing, smoothing, rubbing or otherwise applying the formulation to the skin, hair and/or nails of the animal wherein the formulation contains the weight of dendritic polymer in the formulation from about 0.0001% by weight to about 50% by weight.

83. A method of calibrating a substrate which comprises preparing a solution (about 1 picogram/mL to about 100 mg/mL) of a dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60, applying the solution to a nanometer substrate for size comparison standards, and visualizing the substrate by optical, force or electron microscopy to reference the unknown substrate'"'"'s size relative to the dendritic polymer and/or determining the pore size of the substrate or filter by determining which size dendritic polymer passes through the pore or filter of the substrate.

84. A method of applying a disinfectant to a surface which comprises spraying, wiping, or applying to the surface a dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 as solution or in solvent, with or without the presence of other additives for (M) such as dyes, fragrances, antibacterials, surfactants and/or demulsifiers.

85. A kit comprising a dendritic polymer of Formula (I) as claimed in any one of claims 1-55 and 60 for use in an assay as a biomarker reagent, molecular probe, transfection reagent, or environmental assay reagent together with any other components required for such assay either in separate containers or obtained separately and with instructions on use.

86. A dendritic polymer of Formula (I) as claimed in claim 1 or 2 wherein the core (C) is a spherical shape and is reacted with four reagents having an (EX) or (BR) or both a (EX) and (BR) that are spherical shapes such that the following number of reagents can react:

87. A dendritic polymer of Formula (I) as claimed in claim 1 or 2 wherein the core (C) is a spherical shape and is reacted with four reagents of a conical shape having an (EX) or (BR) or both a (EX) and (BR) such that the following number of reagents can react:

Where, in the equations below;

R=radius of core

h=height of cone (shell reagents)

r=radius of cone (shell reagents) base=the in-radius of tetrahedron base

r′

=in-radius of tetrahedron=R+h

a=length of side of tetrahedron

$\begin{array}{cc}{r}^{\mathrm{\prime <br><br>}}=h+R=\frac{1}{12}<br><br>\sqrt{6}<br><br>a<br><br><br><br>\mathrm{Then},& \mathrm{Equation}<br><br>\text{\hspace{1em}<br><br>}<br><br>1\\ a=2<br><br>\sqrt{6}<br><br>\left(h+R\right)<br><br><br><br>\mathrm{Thus},& \mathrm{Equation}<br><br>\text{\hspace{1em}<br><br>}<br><br>2\\ r=\frac{1}{6}<br><br>\sqrt{3}<br><br>a=\frac{1}{6}<br><br>\sqrt{3}*2<br><br>\text{\hspace{1em}<br><br>}<br><br>\sqrt{6}<br><br>\left(h+R\right)=\sqrt{2}<br><br>\left(h+R\right)& \mathrm{Equation}<br><br>\text{\hspace{1em}<br><br>}<br><br>3\end{array}$

If, r≦

√

{square root over (2)}(h+R), there will be enough space to put four or more shell reagents around the core.

88. A process for preparing the dendritic polymers of Formula (I) as defined in claim 1 which comprises:

A. Reacting, as a one pot reaction, (C) with reactive (BR) precursors (for example iminodiacetic acid, primary amine protected diethylenetriamine (DETA), iminodialkyl nitriles, iminodialkyl phosphonic acids, imino dialkyl halides [e.g. bis(2-chloroethyl)amine], diethanol amine, secondary diamines such as dialkylamines, diallylamines, diarylamines, iminodialkynes, iminoalkyleneamines [e.g., bis(hexamethylenetriamine)]) or preformed (BR) reagents [for example tris(2-aminoethyl)amine (TREN), tris(hydroxymethyl)aminomethane (TRIS), acetylene di- or tri-epoxy moieties], or hydroxy, mercapto or amino (FF) dendrons, in a solvent, at a temperature from about 0°

to 100°

C. until completion of the reaction, to provide the dendritic polymers of Formula (I) where m=0 and q=1-4000;

B. Reacting the dendritic polymer made in Step A by using orthogonal chemistry on the (TF) to add additional (BR) moieties to provide higher generations of homo/hetero compositional (BR) containing dendritic polymers of Formula (I), where m=0 or 1-2000 and q=1-4000;

C. Protecting, by ketone solvent protection, of either reactive (BR) precursors or (BR) possessing secondary and/or primary amines, allowing reaction of only secondary amine sites with reactive (C) or reactive (TF), or when only primary amines are present in the preformed (BR), one or more of these primary amine moieties may be protected with ketone solvent and the other unprotected primary amines may be allowed to react with appropriate (C) or (TF) to provide the dendritic polymers of Formula (I), where m=0 or 1-2000 and q=1-4000;

D. Reacting the dendritic polymer made in Step A by nucleophilic reaction (Michael'"'"'s addition) of an alkylamine with an alkyl acrylate (such as methyl acrylate) to form aminoalkyl ester linkages, followed by reaction of the ester with alkleneamines or (EX) or other (BR) of Formula (I) to provide the dendritic polymers of Formula (I), where m=0 or 1-2000 and q=14000;

E. Reacting the dendritic polymer made in Step A by converting either (C) or (BR) possessing primary amine (TF) groups into pyrrolidone ester groups by reaction with dimethylitaconate (DMI);

followed by reaction of this ester with primary amines or partially protected primary polyamines to provide linkages to (BR) or (TF) moieties of Formula (I), to provide the dendritic polymers of Formula (I) where m=0 or 1-2000 and q=14000;

F. Reacting the dendritic polymer made in Step A by free radical addition of thiol containing preformed (BR) reagents or reactive (BR) precursors to provide (C) or (BR) possessing allylic or olefinic groups of Formula (I), to provide the dendritic polymers of Formula (I), where m=0 or 1-2000 and q=14000;

G. Reacting, either by sequential or concurrent addition, by 1,3-dipolar cyclo-addition of (C) containing from 1 to N_c azides or alkynes and (BR) containing from 1 to N_b−

1 azides or alkynes where the (C) and (BR) have only one of an azide or alkyne present per (C) or (BR) and must have both an azide and alkyne present between them, and the azide containing (C) and (BR) are produced by nucleophilic ring-opening of epoxy rings with azide ions, followed by reaction of these reactive groups to provide triazole linkages to new (BR) or (TF) moieties of Formula (I), to provide the dendritic polymers of Formula (I) where m=1-2000 and q=0 or 1-4000; and

H. Reacting (EX) as a part of Steps B-G to insert (EX) after any (BR) or (C) to provide the dendritic polymers of Formula (I), where m=1-2000.

89. A process to prepare the dendritic polymers of Formula (I) as defined in claim 1 or 2 by an acrylate-amine reaction system which comprises:

A. Reacting an acrylate functional core with an amine functional extender, such as shown below;

(C)+(EX)→

(C)(EX)(TF)

 

where (C)=an acrylate functional core such as trimethylolpropane triacrylate (TMPTA);

(EX)=an amine functional extender such as piperazine (PIPZ); and

(TF)=amine; and

B. Reacting an amine functional extended core reagent of (C) (EX) (TF1) with an acrylate functional branch cell reagent (BR) as shown below

(C)(EX)(TF1)+(BR)→

(C)(EX)(BR)(TF2)

 

where (C)=trimethylolpropane triacrylate (TMPTA);

(EX)=piperazine (PIPZ);

(TF1)=Amine;

(BR)=trimethylolpropane triacrylate (TMPTA); and

(TF2)=Acrylate; and

wherein for both Steps A and B;

the addition of an extender (EX) group to a core, the mole ratio of (EX)/(C) is defined as the moles of extender molecules (EX) to the moles of reactive functional groups on the simple core, scaffolding core, super core, or current generation structure (i.e. N_c) where an excess of (EX) is used when full coverage is desired;

the addition of a branch cell (BR) to a simple core, scaffolding core, super core, or current generation structure (BR)/(C) is defined as the moles of branch cell molecules (BR) to the moles of reactive functional groups on the simple core, scaffolding core, super core, or current generation structure (i.e. N_c) where an excess of (BR) is used when full coverage is desired; and

the level of addition of branch cells (BR) or extenders (EX) to a core, scaffolding core, super core or current generational product can be controlled by the mole ratio added or by N-SIS.

90. A process to prepare the dendritic polymers of Formula (I) as defined in claim 1 or 2 by ring-opening reaction system which comprises:

A. Reacting an epoxy functional core with an amine functional extender, such as shown below;

(C)+(EX)→

(C)(IF1)(EX)(TF1)

 

where (C)=an epoxy functional core such as pentaerythritol tetraglycidyl ether (PETGE);

(IF1)=Internal hydroxyl (OH);

(EX)=piperazine (PIPZ);

(TF1)=Amine; and

B. Reacting an amine functional extended core reagent (C) (IF1) (EX) (TF1) with an epoxy functional branch cell reagent such as shown below;

(C)(IF)(EX)(TF1)+(BR)→

(C)(IF1)(EX)(IF2)(BR)(TF2)

 

where (C)=pentaerythritol tetraglycidyl ether (PETGE);

(IF1)=Internal functionality moiety as defined in claim 1 such as OH;

(EX)=an extender moiety as defined in claim 1 such as piperazine (PIPZ);

(TF1)=Amine;

(BR)=an epoxy functional branch cell reagent such as pentaerythritol tetraglycidyl ether (PETGE); and

(IF2)=Internal functionality moiety as defined in claim 1 such as OH;

(TF2)=Amine; and

wherein for both Steps A and B;

the addition of an extender (EX) group to a core, the mole ratio of (EX)/(C) is defined as the moles of extender molecules (EX) to the moles of reactive functional groups on the simple core, scaffolding core, super core, or current generation structure (i.e. N_c) where an excess of (EX) is used when full coverage is desired;

the addition of a branch cell (BR) to a simple core, scaffolding core, super core, or current generation structure (BR)/(C) is defined as the moles of branch cell molecules (BR) to the moles of reactive functional groups on the simple core, scaffolding core, super core, or current generation structure (i.e. N_c) where an excess of (BR) is used when full coverage is desired; and

the level of addition of branch cells (BR) or extenders (EX) to a core, scaffolding core, super core or current generational product can be controlled by the mole ratio added or by N-SIS.

91. A process to prepare the dendritic polymers of Formula (I) as defined in claim 88 wherein:

N_c=1 to 20;

q=1 to 250;

p=1 to 250; and

m=1 to 250; and

if more than 1 q, p, or m are present, the (IF), (BR), and (EX) moieties may be the same or different; and

(BR) or (EX) may occur alternately with the other moiety or sequentially with multiple groups of (BR) or (EX) occurring in succession.