EP1073902A2 - Naonometerpartikel mit reaktiver schicht - Google Patents

Naonometerpartikel mit reaktiver schicht

Info

Publication number
EP1073902A2
EP1073902A2 EP99953384A EP99953384A EP1073902A2 EP 1073902 A2 EP1073902 A2 EP 1073902A2 EP 99953384 A EP99953384 A EP 99953384A EP 99953384 A EP99953384 A EP 99953384A EP 1073902 A2 EP1073902 A2 EP 1073902A2
Authority
EP
European Patent Office
Prior art keywords
group
monolayer
mixtures
core
particle according
Prior art date
Legal status (The legal status 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 status listed.)
Withdrawn
Application number
EP99953384A
Other languages
English (en)
French (fr)
Inventor
Royce W. Murray
Allen C. Templeton
Michael J. Hostetler
Jeremy J. Pietron
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
University of North Carolina at Chapel Hill
Original Assignee
University of North Carolina at Chapel Hill
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
Application filed by University of North Carolina at Chapel Hill filed Critical University of North Carolina at Chapel Hill
Publication of EP1073902A2 publication Critical patent/EP1073902A2/de
Withdrawn legal-status Critical Current

Links

Classifications

    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
    • G01N33/54313—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being characterised by its particulate form
    • G01N33/54346—Nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0004—Preparation of sols
    • B01J13/0043—Preparation of sols containing elemental metal
    • 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
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
    • G01N33/54353—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals with ligand attached to the carrier via a chemical coupling agent
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/53—Immunoassay; Biospecific binding assay; Materials therefor
    • G01N33/543—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals
    • G01N33/551—Immunoassay; Biospecific binding assay; Materials therefor with an insoluble carrier for immobilising immunochemicals the carrier being inorganic
    • G01N33/553—Metal or metal coated
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
    • G01N33/48—Biological material, e.g. blood, urine; Haemocytometers
    • G01N33/50—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing
    • G01N33/58—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances
    • G01N33/585—Chemical analysis of biological material, e.g. blood, urine; Testing involving biospecific ligand binding methods; Immunological testing involving labelled substances with a particulate label, e.g. coloured latex
    • G01N33/587—Nanoparticles

Definitions

  • the invention generally relates to nanometer-sized particles which have been chemically modified and methods of making the same.
  • nanotechnology relates to the art and science of building molecular materials so that they are capable of functioning as macro-scale structures and/or exhibiting physical and chemical properties which are intermediate between molecular and bulk materials. Applications involving nanotechnology are potentially far reaching. Areas of possible interest relate to, for example, catalysis, molecular electronics, biotechnology, composite materials, solar energy conversion, and the like. Investigative efforts regarding nanotechnology have focused largely on understanding the physical behavior and structure of nanometer-sized materials. Reiss, H., Proceedings of the Welch Foundation 39 th Conference on Chemical Research: Nanophase Chemistry (1995) 49-66 discusses thermodynamic behavior associated with nanophase technology.
  • Nanometer-sized gold particles can be chemically attached to metal surfaces, such as electrodes.
  • the purpose of such experiments is to allow the researcher to add functionality onto the immobilized particles in order to add value to the metal surface.
  • Metal sols are small particles which are insoluble, and thus suspended, in the liquid in which they are dispersed. Numerous recent studies have investigated methods for adding to the complexity of metal sols. For example, Mirkin, C.A., et al., Nature 382 (1996) 607-609, proposes attaching oligonucleotides to gold sols in order to promote aggregation of said sols upon addition of an appropriate complementary oligonucleotide to the sol solution.
  • U.S. Patent No. 4,859,612 to Cole et al. proposes that antibody coated metal sols can interact with an appropriately coated solid phase particle as a means for an immunoassay procedure.
  • Soc, 117:50 (1995) 12537-12548 proposes nanometer- sized gold cores which are stabilized by chemisorbed layers of octane- or hexadecanethiolate. These monolayer-protected gold clusters were found to be highly stable as determined by differential scanning calorimetry techniques.
  • Hostetler, M.J., et al., Langmuir, 12 (1996) 3604-3612 relates to the evaluation of the physical structure of alkanethiolates of various chain lengths adsorbed onto nanometer-sized gold cores. Alkanethiolates with shorter chain lengths were determined to be relatively disordered while materials with longer chain lengths were found to be in the trans zig-zag conformation.
  • the previous three descriptions of the art represent nanometer-sized gold cores covered with simple, non-derivatized alkanethiols, a circumstance that severely limits their applicability.
  • nanometer-sized materials which exhibit specific chemical and physical properties. More particularly, there is a need for such materials which can be tailored for utilization in a number of defined end use applications. It would be particularly desirable if the nanometer-sized particles exhibited flexible chemical behavior as well as
  • the invention relates to a functionalized nanometer- sized particle comprising a core which comprises at least one metal or metal 120 alloy; and a monolayer chemically bonded to the core.
  • the monolayer is formed during the formation of the core and can be modified at any time following formation of the core.
  • the monolayer contains at least one reactive substituent thereon which is coupled to a functional material such that the monolayer becomes chemically modified.
  • the reactive substituent may be 125 selected from a number of groups such as, for example, SH, OH, NH 2 , NH, C0 2 H, SO 3 OH, P0 2 (OH) 2 , BO(OH) 2 , or mixtures thereof.
  • a number of functional materials may be employed such as catalysts, biomaterials, and materials which are chemically, electrochemically, or photochemically active.
  • the particles may be readily
  • the invention in another aspect, relates to a method of making a functionalized nanometer-sized particle.
  • the method comprises providing a nanometer-sized particle comprising: (1) a core which comprises at least one metal or metal alloy and (2) a monolayer chemically bonded to the core, the
  • the nanometer-sized particle is then coupled with a functional material such that the monolayer becomes chemically modified.
  • this method allows for the particle to be modified based on a small subset of reactive substituents, all of which can be readily synthesized or purchased commercially. Adding greater value to said
  • nanometer-sized particle can then be accomplished using a variety of functional materials.
  • FIG. 1 is a representation of a multi-step synthesis of a tripeptide- functionalized monolayer-protected nanometer-sized gold core.
  • FIG. 2a is a graph illustrating the electrochemical characterization of a 10H-(phenothiazine-10)propionic acid-functionalized monolayer-protected nanometer-sized gold core. Specifically, the figure illustrates the cyclic 150 voltammetry of 0.8 mM 70H-(phenothiazine-10)propionic acid (-) in 2:1 toluene/acetonitrile (v/v) at 10OmV/s; and
  • the invention relates to a functionalized nanometer-sized particle.
  • the functionalized nanometer-sized particle comprises a core
  • the core preferably has a diameter ranging from about 1 nm to about 999 nm, more preferably from about 1 nm to about 100 nm; even more preferably from about 1 nm to about 20 nm; and most preferably from about 1 nm to about 7 nm.
  • a monolayer is chemisorbed or chemically bonded to the core. The monolayer
  • 170 contains at least one reactive substituent as described further herein.
  • the reactive substituent(s) on the monolayer is/are coupled to a functional material so as to chemically modify the monolayer.
  • metals and metal alloys may be used in the core.
  • the metal or metal alloy is selected from the group consisting of
  • a semiconducting material a metal oxide material, a Group VIIIA element, a
  • the metal or metal alloy is selected from the group consisting of a Group VIIIA element, a Group IB element, alloys thereof, and mixtures thereof. Examples of elements which may be used include, but are not limited to, gold,
  • Examples of semiconducting materials include, but are not limited to, cadmium sulfide, indium phosphide, and other Group lll-V materials.
  • Example of oxide materials include, but are not limited to, titanium oxide (titania), aluminum oxide (alumina), tin oxide, and iron oxide.
  • the shape of the core is not restricted to any particular 185 geometry, thus, for example, rods, spheres, cuboctahedra, and truncated octahedra, will all satisfy the conditions stated herein.
  • the term "monolayer” may be defined as a layer preferably having a thickness ranging from about 0.4 nm to about 100 nm, and more preferably 1.0 to 20 nm.
  • the monolayer is typically formed during the formation of the core, and the monolayer can be modified at any point following formation of the core.
  • the monolayer which is adsorbed or chemically bonded to the core may comprise a number of materials. Examples of these materials include, but are not limited to, organic compounds (e.g., alkanethiols, arylthiols, vinylthiols,
  • inorganic compounds e.g., alkyl borates, alkyl phosphonates, alkyl silicates), organometallic compounds (e.g., ferrocenethiol); biochemical compounds (e.g., cysteine, albumin, coenzyme A), and mixtures thereof.
  • the monolayer include, for example, branched molecules
  • the monolayer may comprise an alkanethiol or an alkanethiol derivative.
  • Exemplary alkanethiols include those having between 2 and 23 carbon atoms.
  • the monolayer contains at least one reactive substituent.
  • reactive substituent refers to those substituents which are chemically active so that, upon reaction with a functional material, part of the reactive substituent remains with the
  • reactive substituents include, but are not limited to, SH, OH, NH 2 , NH, C0 2 H, S0 3 OH, P0 2 (OH) 2 , BO(OH) 2 , and mixtures thereof. More preferably, OH, NH, C0 2 H, NH 2 , and mixtures thereof are employed. Examples of compounds which may be present
  • R is selected from the group consisting of an organic compound, an inorganic compound, an organometallic compound, a biochemical compound, and mixtures thereof;
  • E is selected from the group consisting of S, O, NH, COO,
  • n is an integer ranging from 1 to 5 (more preferably from 1 to 2); and x is an integer ranging from 1 to 10 (more preferably from 1 to 3). More preferably, E is selected from O, NH, C0 2 , NH 2 , and mixtures thereof.
  • the chemically modified monolayer may also include partially reactive and nonreactive compounds or materials.
  • nonreactive compounds or materials may be used in any ratio so long as at least one reactive compound or material is present on the monolayer.
  • the monolayer is preferably chemically bonded to the core by various types of bonds.
  • bonds include, but are not limited to, core- element-sulfur bonds, core-element-oxygen-bonds, core-element-boron, core-
  • the monolayer is chemically bonded to the core by various core-element-sulfur bonds.
  • core-element refers to any element of which the core is composed.
  • the monolayer is coupled to a functional material such that the monolayer is chemically modified.
  • the term "coupled” may be interpreted to mean that the monolayer and the functional material are linked via formation of a new chemical bond. Examples, include, but are not limited to amide, thioester, and ester-forming reactions known in the art.
  • Examples of functionalities which may be present on the functional materials include, but are not limited to, SH, OH, NH 2 , NH, C0 2 H, S0 3 OH, P0 2 (OH) 2 , BO(OH) 2 , and mixtures thereof.
  • Examples of reactive substituents include, but are not limited to, SH, OH, NH 2 , NH, C0 2 H, S0 3 OH, P0 2 (OH) 2 , BO(OH) 2 , and mixtures thereof. More preferably, OH, NH, C0 2 H, NH 2 , and mixtures thereof
  • the functional material may also comprise at least one compound having the general formula:
  • R n (EH) x wherein R is selected from the group consisting of an organic compound, an inorganic compound, an organometallic compound, a biochemical compound,
  • E is selected from the group consisting of S, O, NH, COO,
  • n is an integer ranging from 1 to 5 (more preferably from 1 to 2); and x is an integer ranging from 1 to 10 (more preferably from 1 to 3). More preferably, E is selected from O, NH, C0 2 , NH 2 , and mixtures thereof. It should be emphasized that the
  • the functional material may be present in the form of a number of structures which possesses functionality in the manner described herein.
  • the functional material may be a catalyst, a biomaterial, a material which is electrochemically active, or combinations thereof.
  • the functional material may also be one which has a low-lying excited state which is capable of undergoing
  • the functional material may also be selected such that the nanometer-sized particle is soluble in a solvent.
  • soluble may be defined to mean the particles being dispersed or dissolved in the solvent.
  • suitable solvents include aqueous or organic solvents.
  • the invention relates to a method of making a functionalized nanometer-sized particle.
  • the method comprises providing a nanometer-sized particle comprising a core which comprises at least one metal or metal alloy, and a monolayer adsorbed onto the core.
  • the monolayer includes at least one reactive substituent.
  • the nanometer-sized particle is then
  • a number of functional materials may be used in the above method. Examples of these materials include, but are not limited to, spin labels (e.g., 4- amino-TEMPO), metal ligands (e.g., 4-(aminomethyl)-pyridine), amino acids
  • chromophores and fluorophores e.g., 1- aminopyrene and 2-naphthaleneethanol
  • ionophores e.g., 2-(aminomethyl)-15- crown-5
  • molecules susceptible to functional group conversion e.g., benzyl amine
  • electroactive molecules e.g., ferrocene methanol, " OH-(phenothiazine- 10) propionic acid, anthraquinone-2-carboxylic acid
  • sugars e.g., ⁇ -D-glucose
  • nucleotides e.g., uridine
  • the coupling step is preferably carried out in the presence of a reagent which may be, for example, a phophonium reagent, a facilitating reagent, as well as mixtures thereof.
  • a reagent which may be, for example, a phophonium reagent, a facilitating reagent, as well as mixtures thereof.
  • the facilitating reagent may be selected from a base, a catalyst, and mixtures thereof.
  • Preferred bases include various pyridine
  • components which may be employed during the coupling step include, but are not limited to, BOP (benzotriazol-1- yloxytris(dimethylamino)phosphonium hexafluorophosphate); HOBt (1- hydroxybenzotriazole); NMM (4-methylmorpholine); DMAP (4- dimethylaminopyridine); and mixtures thereof
  • the invention in another aspect, relates to a method of analyzing a nanometer-sized particle.
  • the method comprises subjecting a nanometer-sized particle as defined herein to an analytical technique such that the composition of the functional materials of the monolayer on the particle are determined.
  • an analytical technique such that the composition of the functional materials of the monolayer on the particle are determined.
  • a number of analytical techniques may be employed in this method. Examples of
  • such techniques include, but are not limited to, NMR spectroscopy, electrochemical techniques, fluorescent emission spectroscopies, and infrared spectroscopies. Examples
  • 345 are those that are unique to each functionalized monolayer-protected nanometer-sized gold core (an infrared spectra of a nanometer-sized gold core which is stabilized by chemisorbed layers of dodecanethiolate was used for background subtraction).
  • BOP benzotriazol-1- yloxytris(dimethylamino)phosphonium hexafluorophosphate
  • HOBt 1- hydroxybenzotriazole
  • NMM 4-methylmorpholine
  • DMAP dimethylaminopyridine
  • 4-amino-TEMPO 4-amino-2, 2,6,6-
  • CD 2 CI 2 ⁇ (ppm) - 0.9 (br, 17 H), 1.3 (br, 150 H), 2.75 (br, 0.2 H), 4.0 (br, 2 H), 4.1 (br, 2 H), 6.8 (br, 5.9 H), 7.1 (br, 5.9 H)
  • IR 2851 (d + ), 2921 (d ), 1817, 1733, 1700, 1633, 1616, 1491 , 1411 , 843, 782, 764, 742 cm "1 .
  • the electrochemistry of this MPC derivative is shown in Figure 3a. The percent conversion to number 495 coupled ratio was determined to be 65/7.4.
  • Cyclic voltammetry (seen in Figure 2) was performed with a BAS 100B electrochemical analyzer sold by Bioanalytical Systems, Inc., located in West Lafayette, Indiana. A platinum 3 mm diameter working electrode was polished with 0.5 ⁇ m diamond (Buehler) paste followed by rinsing with water, ethanol, and
  • Thin-layer coulometry (as seen in Figure 2b) was performed using a BAS 590 100B electrochemical analyzer.
  • a 4.3 mm diameter Pt working electrode was polished with 0.5 ⁇ m of diamond (Buehler) paste followed by rinsing with water, ethanol, and acetone and toluene prior to each experiment.
  • a Pt wire counter electrode and Ag wire quasi-reference electrode (AgQRE) resided in a locally designed thin-layer cell as defined in Reilley, C.N., Pure Appl. Chem. 18 (1968) 595 137.
  • a Mitutoyo digital micrometer (1-2", 0.00005" resolution) sold by Mitutoyo

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  • Health & Medical Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Immunology (AREA)
  • Biomedical Technology (AREA)
  • Hematology (AREA)
  • Molecular Biology (AREA)
  • Urology & Nephrology (AREA)
  • General Physics & Mathematics (AREA)
  • Physics & Mathematics (AREA)
  • Biochemistry (AREA)
  • Food Science & Technology (AREA)
  • Medicinal Chemistry (AREA)
  • Microbiology (AREA)
  • Analytical Chemistry (AREA)
  • Cell Biology (AREA)
  • General Health & Medical Sciences (AREA)
  • Biotechnology (AREA)
  • Pathology (AREA)
  • Nanotechnology (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
EP99953384A 1998-04-20 1999-04-09 Naonometerpartikel mit reaktiver schicht Withdrawn EP1073902A2 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US62863 1987-06-16
US6286398A 1998-04-20 1998-04-20
PCT/US1999/007823 WO1999061911A2 (en) 1998-04-20 1999-04-09 Nanometer particles containing a reactive monolayer

Publications (1)

Publication Number Publication Date
EP1073902A2 true EP1073902A2 (de) 2001-02-07

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EP99953384A Withdrawn EP1073902A2 (de) 1998-04-20 1999-04-09 Naonometerpartikel mit reaktiver schicht

Country Status (4)

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EP (1) EP1073902A2 (de)
AU (1) AU6016999A (de)
CA (1) CA2329859A1 (de)
WO (1) WO1999061911A2 (de)

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US6316100B1 (en) 1997-02-24 2001-11-13 Superior Micropowders Llc Nickel powders, methods for producing powders and devices fabricated from same
GB0025414D0 (en) 2000-10-16 2000-11-29 Consejo Superior Investigacion Nanoparticles
US6653653B2 (en) 2001-07-13 2003-11-25 Quantum Logic Devices, Inc. Single-electron transistors and fabrication methods in which a projecting feature defines spacing between electrodes
US6483125B1 (en) 2001-07-13 2002-11-19 North Carolina State University Single electron transistors in which the thickness of an insulating layer defines spacing between electrodes
GB0126236D0 (en) 2001-11-01 2002-01-02 Univ East Anglia Photosensitiser functionalised nanoparticles
US6673717B1 (en) 2002-06-26 2004-01-06 Quantum Logic Devices, Inc. Methods for fabricating nanopores for single-electron devices
GB0313259D0 (en) * 2003-06-09 2003-07-16 Consejo Superior Investigacion Magnetic nanoparticles
FR2859117B1 (fr) * 2003-08-27 2006-02-03 Commissariat Energie Atomique Utilisation de nanoparticules a coeur metallique et double enrobage organique en tant que catalyseurs et nanoparticules utiles comme catalyseurs
JP5117191B2 (ja) * 2004-10-01 2013-01-09 ミダテック リミテッド 抗原及びアジュバントを含むナノ粒子、並びに免疫原性構造
TW200640596A (en) 2005-01-14 2006-12-01 Cabot Corp Production of metal nanoparticles
US7824466B2 (en) 2005-01-14 2010-11-02 Cabot Corporation Production of metal nanoparticles
WO2006076608A2 (en) 2005-01-14 2006-07-20 Cabot Corporation A system and process for manufacturing custom electronics by combining traditional electronics with printable electronics
CN1305977C (zh) * 2005-03-04 2007-03-21 北京化工大学 用转移法对纳米级无机颗粒表面改性的方法

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CA2026409C (en) * 1989-09-29 2004-11-09 Ernest G. Schutt Method of producing a reagent containing a narrow distribution of colloidal particles of a selected size and the use thereof
GR1000686B (el) * 1989-11-16 1992-10-08 Ortho Diagnostic Systems Inc Μεθοδος παραγωγης ενος αντιδραστηριου κολλοειδους μεταλλου που περιεχει κολλοειδη τεμαχιδια μεταλλου με προκαθορισμενο μεγεθος. εθος.

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Title
See references of WO9961911A3 *

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CA2329859A1 (en) 1999-12-02
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WO1999061911A2 (en) 1999-12-02

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