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WO1997039041A1 - Films monocouches dendrimeres - Google Patents

Films monocouches dendrimeres Download PDF

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Publication number
WO1997039041A1
WO1997039041A1 PCT/US1997/006513 US9706513W WO9739041A1 WO 1997039041 A1 WO1997039041 A1 WO 1997039041A1 US 9706513 W US9706513 W US 9706513W WO 9739041 A1 WO9739041 A1 WO 9739041A1
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WO
WIPO (PCT)
Prior art keywords
dendrimer
substrate
monolayer
self
dendrimers
Prior art date
Application number
PCT/US1997/006513
Other languages
English (en)
Inventor
Richard M. Crooks
Antonio J. Ricco
Mona Wells
Original Assignee
The Texas A & M University System
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US08/639,049 external-priority patent/US6312809B1/en
Application filed by The Texas A & M University System filed Critical The Texas A & M University System
Priority to AU26765/97A priority Critical patent/AU2676597A/en
Publication of WO1997039041A1 publication Critical patent/WO1997039041A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D201/00—Coating compositions based on unspecified macromolecular compounds
    • C09D201/005—Dendritic macromolecules
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures

Definitions

  • the present invention relates to a substrate having a dendrimer film thereon, and in particular, a dendrimer monolayer film that is covalently bonded to the surface, which film can be used, for example, as a chemically sensitive surface.
  • Dendrimers are three dimensional manmade molecules which, as illustrated in Figure 1, have a three- dimensional, spherical or ball shape.
  • Dendrimer macromolecules are generally produced in one of two ways. See, for example, "Preparation of Polymers with Controlled Molecular Architecture. A New Convergent Approach to Dendritic Macromolecules, " Hawker et al . , J. Am Chem. Soc, 1990, 112, pp 7638-7747, which is incorporated herein by reference! The first of these method is called the "divergent" approach. Such methods relate to the outward growth of the dendrimers from the center core in producing dendritic macromolecules.
  • a second method for producing dendrimers is a convergent approach. The convergent method, the individual branches which make up the dendrimer are produced and these branches are then connected together so as to form the resulting dendrimer.
  • Dendrimers have generated a great deal of excitement largely due to their hollow, three-dimensional ball-like shape. It has been proposed to employ material "inside” the dendrimers which would allow the resulting material to be used in a variety of applications such as genetic therapy, drug delivery and even computer chips. For example, such "balls” can carry genetic materials into cells to repair birth defects. Alternatively, dendrimers can act as a delivery system for drugs.
  • dendrimers could be introduced onto a surface of a substrate.
  • the art has not been able to successfully bond, and in particular, covalently bond, dendrimers onto the surface of the substrate.
  • the substrate has reactive functional groups secured thereto and at least one dendrimer monolayer is covalently bonded to the surface through the reactive functional groups.
  • the monolayer film comprises dendrimer branches or dendrons which are "grown" from the substrate is provided.
  • the monolayer is covalently bonded to the substrate by way of the reactive functional groups.
  • Figures 4, 5, 6a and 6b are graphical representations of data presented in the examples according to the present invention.
  • the dendrimer monolayer films of the present invention which comprise dendrimers or branches of dendrimers can be introduced onto any of a variety of substrates.
  • substrates can comprise insulators, conductors, or semiconductors.
  • said substrates can comprise metals or nonmetals from the periodic table, polymers, and the like.
  • suitable substrates include gold, aluminum, aluminum oxide, gallium-arsenide, copper, silver and poly(acrylic acid) .
  • the substrate have reactive functional groups secured thereto.
  • reactive functional groups are selected so as to be reactive with a corresponding groups of the dendrimer or dendron.
  • the corresponding groups are the terminal end groups on the outside of the dendrimer.
  • the corresponding group is the "base group" of the branch.
  • suitable reactive functional groups for the substrate include carboxylic groups, hydroxy groups, and epoxy groups with carboxylic groups being preferred.
  • carboxylic groups hydroxy groups
  • epoxy groups with carboxylic groups being preferred.
  • any combination of groups suitable for reacting so as to covalently bond the monolayer onto the surface of a substrate can be employed.
  • the reactive functional groups can be introduced onto the substrate by any art-recognized method.
  • a self-assembled monolayer including the reactive functional groups (or precursor thereof) is introduced onto the substrate and the dendrimer or dendrimer branches are covalently bonded thereto.
  • Self-assembled monolayers are known in the art. See, for example, DuBois et al . , Annu. Rev. Phys. Chem., 1992, 43, p. 437 et seq. which is incorporated herein by reference.
  • self-assembled monolayers relate to a monolayer film which is comprised of molecules that attach themselves to a substrate and align themselves parallel to each other with each molecule extending from the substrate. Such molecules are capable of forming well-ordered monolayers on a variety of surfaces.
  • organomercaptans and in particular, ⁇ -functionalized n-alkanethiols are organomercaptans and in particular, ⁇ -functionalized n-alkanethiols. These compounds preferably have from 4-40 carbon atoms, more preferably 10-20, and still more preferably about 11 carbon atoms . While self-assembled monolayers produced from such compounds can be employed in this invention, it is equally applicable to the wide variety of SAMs in use today. For example, both unpolymerized and polymerized SAMs can be use. Polymerized SAMs are discussed in Kim et al . "Polymeric Self-Assembling Monolayer. 1.
  • the primary requirement is that they include reactive functional groups on the surface thereof.
  • the functional groups associated with the SAMs are subject to the same requirements as those discussed above, i.e., capable of reacting with the terminal end groups of a dendrimer or a starting group of a dendrimer branch, so as to covalently bond the dendrimer monolayer onto a surface of a substrate.
  • reactive functional groups can be introduced in producing the molecules used in making the SAMs or, the surface of the SAMs can be modified subsequent to bonding onto the substrates .
  • Techniques for modifying the surface of SAMs are recognized in the art. See, for example, Duevel et al, R . M. Anal . Chem . , 1992, 4, p. 337; and the previously cited Kim et al article from J. Am . Chem . Soc , 1995, 117, which are incorporated by reference.
  • the monolayer of the present invention can be formed either of two ways.
  • preformed dendrimers can be covalently bonded to the reactive functional groups in a manner such as that illustrated by Figure 1.
  • any dendrimer having suitably reactive endgroups can be introduced onto the surface.
  • Dendrimers for use in this embodiment can be produced, for example, by either the divergent or convergent methods for forming the dendrimers.
  • PAMAM poly(amidoamine)
  • suitable dendrimers are discussed in the Hawker et al . article discussed above.
  • the size of the dendrimer is not critical, i.e., dendrimers of any generation can be employed in this invention. Specific examples include PAMAM dendrimers of generations G0-G8. Further, suitable dendrimers can be commercially obtained from, for example, Dendritech Inc.
  • the dendrimer can be covalently bonded onto the surface of the substrate through the reaction of the terminal end groups of the dendrimer with the reactive functional groups.
  • the terminal end groups are amino groups and the functional groups are carboxylic acid groups
  • suitable techniques such as chloroformate-mediated linking reaction can be employed.
  • the dendrimer layer comprises' a plurality of dendrimer branches or dendrons which are "grown" on the desired surface.
  • the formation of the monolayer in this regard occurs according to either the divergent or convergent approach for forming dendrimers and results in the formation of a monolayer that comprises dendrons rather than the entire dendrimer macromolecule.
  • Figure 2 illustrates a divergent technique for forming dendrons on the surface of a substrate while Figure 3 illustrates the convergent approach.
  • the divergent approach involves the addition of each generation in discrete steps, such that the dendrimer increases in incremental size like an onion.
  • Examples of art-recognized techniques in this regard include both solution phase synthetic techniques and Merrifield solid-state synthetic techniques.
  • the convergent approach involve the use of protection/deprotection schemes to synthesize dendrons which are subsequently joined to a central "core.”
  • This technique can involve, for example, the coupling of dendrons to active sites using a zero length heterobifunctional linking agent.
  • the dendrons can include those from an outside source, e.g., inveigle dendrons, or an be produced by techniques recognized in the art, e.g., bulk-phase techniques. Irrespective of the technique employed, upon the formation of the monolayer, the outer surface of the monolayer has a relatively corrugated profile.
  • dendrimer layers can be effectively introduced onto the substrate.
  • the dendrimer layers can be bonded to each other as long as the innermost layer has end groups on the surface thereof which can react with the terminal end groups of the dendrimers to be deposited.
  • Dendrimer monolayer films according to the present invention represent a new type of interfacial architecture.
  • the voids within the dendrimer superstructure can serve as endoreceptors while the terminal functional groups of the dendrimers serve as exoreceptors. Because of this, the composite structures of the present invention can be readily employed in chemical sensing applications.
  • the monolayer films of the present invention provide the best of both worlds, i.e., the advantages of three-dimensional dendrimeric structure and increased practical applicability because such structures are covalently bonded to a substrate. That is, while the structures can be employed in any of the traditional applications for dendrimers, they can also be effectively employed in a variety of additional applications such as chemical sensing.
  • the surface of the resulting dendrimer monolayer film can be altered so as to increase the utility of the invention.
  • the techniques for alte_ing the surfaces of dendrimers in this regard as the same as those recognizing in the art for altering the surfaces of nonconfined dendrimers. As such, they need not be described in detail here.
  • the present invention will now be described in the form of certain examples. However, these examples should be considered solely as illustrative of the present invention and, in no way, should limit the invention.
  • PAMAM Poly(amidoamine) dendrimers were linked to a mercaptoundecanoic acid (MUA) self-assembled monolayer (SAM) via amide bond formation by the method of Figure 1.
  • MUA mercaptoundecanoic acid
  • SAM self-assembled monolayer
  • Figure 4 shows the amide and carbonyl region of these spectra.
  • Example 2 Because dendrimers of different size and chemical composition may prove suitable for integration into array-based chemical sensors, it is desirable to provide surfaces of varying chemical composition. To illustrate this, a methyl ester-terminated dendrimers using the Michael addition of methyl acrylate to the primary amine terminal groups of surface-confined dendrimers was prepared. Following conversion, the characteristic signature of the methyl ester in the carbonyl region of the infrared spectrum (1720-1740cm "1 ) was observed.
  • Figure 5 illustrates the relationship between surface reactivity, gauged by the area of this carbonyl band, and the square of the dendrimer radius (r d 2 ) .
  • the graph illustrates two important points. First, below the threshold at which PANAM dendrimers adopt a globular geometry (GO and G2) , the dendrimer films show no reactivity because all or most of the outer functional groups react with the surface during attachment. Second, above the threshold at which PANAM dendrimers adopt a globular geometry (G4-G8) , the number of dendrimer film reactive sites increases linearly with r d 2 , indicating that methyl ester conversion is proportional to the surface area of the surface-confined dendrimer spheroids. This is consistent with the three-dimensional evolution of film structure.
  • Example 3 To determine the suitability of dendrimer surfaces as chemically sensitive interfaces, we sequentially dosed dendrimer-modified surface acoustic wave (SAW) mass balances with volatile organic compounds (VOCs) having different functional groups (Figure 6) .
  • Figure 6a is an example of unprocessed data from a typical SAW experiment. It illustrates how the dendrimer-modified device response possesses three of the essential attributes for an ideal chemical sensor: (1) the response to dosants is very rapid, and there is no detectable permeation transient, (2) the device signal- to-noise ratio is excellent, and (3) the response is typically completely reversible.
  • FIG. 6b summarizes the results from vapor-phase dosing of dendrimer-modified surfaces.
  • the response to VOCs decreases in the order acid > alcohols > hydrophobic dosants.
  • This response order is more pronounced for the G4-G8-modified surfaces and is dictated by the PANAM structure which possesses hydrogen-bonding exoreceptors and endoreceptors.
  • the G4-modified surface is the most responsive material probably because, although it is the smallest of the spheroidal dendrimers, its interior endoreceptors are most accessible.
  • GO and G2 dendrimer films are not as effective at discriminating between the three different classes of probes since these surfaces have few or no free amine terminal groups and no coherent endoreceptive ability.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
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Abstract

L'invention concerne un substrat recouvert d'un film monocouche dendrimère. Ledit film peut comporte des dendrimères ou des dendrons (branches de dendrimères). Dans les deux cas, les films monocouches sont liés de manière covalente à la surface voulue. La structure résultante peut être utilisée dans un grand nombre d'applications dont les capteurs chimiques.
PCT/US1997/006513 1996-04-17 1997-04-16 Films monocouches dendrimeres WO1997039041A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU26765/97A AU2676597A (en) 1996-04-17 1997-04-16 Dendrimer monolayer films

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US1569696P 1996-04-17 1996-04-17
US60/015,696 1996-04-17
US08/639,049 US6312809B1 (en) 1996-04-24 1996-04-24 Dendrimer monolayer films
US08/639,049 1996-04-24

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WO1997039041A1 true WO1997039041A1 (fr) 1997-10-23

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006039052A1 (fr) * 2004-09-30 2006-04-13 3M Innovative Properties Company Substrat presentant des dendrimeres fixes sur ce substrat
EP1421216A4 (fr) * 2001-09-01 2006-05-17 Samsung Electronics Co Ltd Procede pour fabriquer une biopuce en hydrogel au moyen d'un derive de polyethyleneglycol etoile comportant un groupe epoxy
US7253004B2 (en) 2001-07-19 2007-08-07 Sony Deutschland Gmbh Chemical sensors from nanoparticle/dendrimer composite materials
US8828733B2 (en) 2007-01-19 2014-09-09 Cantimer, Inc. Microsensor material and methods for analyte detection

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171264A (en) * 1990-02-28 1992-12-15 Massachusetts Institute Of Technology Immobilized polyethylene oxide star molecules for bioapplications

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5171264A (en) * 1990-02-28 1992-12-15 Massachusetts Institute Of Technology Immobilized polyethylene oxide star molecules for bioapplications

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
ANAL. CHEM., Feb. 1992, Vol. 64, DUEVEL R.V. and R.M. CORN, "Amide and Ester Surface Attachment Reactions for Alkanethiol Monolayers at Gold Surfaces as Studied by Polariziation Modulation FTIR", pages 337-342. *
J. AM. CHEM. SOC., Apr. 1995, Vol. 117, KIM T. et al., "Polymeric Self-Assembled Monolayers", pages 3963-3967. *
TET. LETT. 1, 9 Dec. 1994, Vol. 35, No. 51, KIM T. et al., "Polymeric Self-Assembling Monolayers", pages 9501-9504. *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7253004B2 (en) 2001-07-19 2007-08-07 Sony Deutschland Gmbh Chemical sensors from nanoparticle/dendrimer composite materials
EP1421216A4 (fr) * 2001-09-01 2006-05-17 Samsung Electronics Co Ltd Procede pour fabriquer une biopuce en hydrogel au moyen d'un derive de polyethyleneglycol etoile comportant un groupe epoxy
US7695910B2 (en) 2001-09-01 2010-04-13 Samsung Electronics Co., Ltd. Method for manufacturing hydrogel biochip by using star-like polyethylene glycol derivative having epoxy group
WO2006039052A1 (fr) * 2004-09-30 2006-04-13 3M Innovative Properties Company Substrat presentant des dendrimeres fixes sur ce substrat
JP2008514418A (ja) * 2004-09-30 2008-05-08 スリーエム イノベイティブ プロパティズ カンパニー デンドリマーを結合させた基材
US7556858B2 (en) 2004-09-30 2009-07-07 3M Innovative Properties Company Substrate with attached dendrimers
US8828733B2 (en) 2007-01-19 2014-09-09 Cantimer, Inc. Microsensor material and methods for analyte detection

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