EP0986818A1 - Sources irradiantes radioactives au ruthenium a debit de dose eleve, a usage medical et leur procede d'obtention - Google Patents

Sources irradiantes radioactives au ruthenium a debit de dose eleve, a usage medical et leur procede d'obtention

Info

Publication number
EP0986818A1
EP0986818A1 EP99916898A EP99916898A EP0986818A1 EP 0986818 A1 EP0986818 A1 EP 0986818A1 EP 99916898 A EP99916898 A EP 99916898A EP 99916898 A EP99916898 A EP 99916898A EP 0986818 A1 EP0986818 A1 EP 0986818A1
Authority
EP
European Patent Office
Prior art keywords
ruthenium
carrier
gold
layers
radioactive
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Withdrawn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
EP99916898A
Other languages
German (de)
English (en)
Inventor
Werner Schmidt
Renate Freudenberger
Michael Andrassy
Jürgen ZIEGLER
Detlef Behrend
Andre Hess
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.)
Bebig Isotopentechnik und Umweltdiagnostik GmbH
Original Assignee
Bebig Isotopentechnik und Umweltdiagnostik GmbH
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 Bebig Isotopentechnik und Umweltdiagnostik GmbH filed Critical Bebig Isotopentechnik und Umweltdiagnostik GmbH
Publication of EP0986818A1 publication Critical patent/EP0986818A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/623—Porosity of the layers
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00—Radiation therapy
    • A61N5/10—X-ray therapy; Gamma-ray therapy; Particle-irradiation therapy
    • A61N5/1001—X-ray therapy; Gamma-ray therapy; Particle-irradiation therapy using radiation sources introduced into or applied onto the body; brachytherapy
    • A61N2005/1019—Sources therefor
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61N—ELECTROTHERAPY; MAGNETOTHERAPY; RADIATION THERAPY; ULTRASOUND THERAPY
    • A61N5/00—Radiation therapy
    • A61N5/10—X-ray therapy; Gamma-ray therapy; Particle-irradiation therapy
    • A61N5/1001—X-ray therapy; Gamma-ray therapy; Particle-irradiation therapy using radiation sources introduced into or applied onto the body; brachytherapy
    • A61N5/1002—Intraluminal radiation therapy

Definitions

  • the invention relates to radioactive ruthenium radiation sources with a dose rate of at least 1.5 Gy / min at a distance of 2 mm (water), which consist of an activity carrier and an enclosure of the carrier from a body-compatible material, with a multi-layer system of metals on the carrier and / or alloys are electroplated, in which at least two layers consist of ruthenium-106, and inactive intermediate layers of other metals or alloys are present between the radioactive ruthenium layers.
  • the activity carrier is made with a body-compatible material, e.g. a metal or plastic.
  • the activity carrier can be enclosed by filling it into a capsule and then closing it, or by means of electrodeposition of a cover layer, e.g. made of hard gold.
  • Electrolytes but is halogen-free, contains at least 1.5 g / 1 sulphate ions and has a pH of at most 4.
  • Ruthenium radiation sources for ophthalmology on the market are made by electrolytic deposition of ruthenium made from commercially available radioactive ruthenium (III) chloride solutions.
  • the thin layers obtained in this way with dose rates of 0.1 to 0.5 Gy / min. are sufficient for the use of the radiation source as an eye applicator in the tumor treatment of the eye.
  • these radiation sources are not suitable because they do not have the necessary dose rate due to the achievable only thin layers.
  • the object of the invention was therefore to provide radioactive ruthenium radiation sources for medical applications which should have a high dose rate and which, despite the necessary thickness of the active ruthenium layer, should have the necessary flexibility and geometry, for example in the intravascular treatment of vascular anomalies to be able to be used.
  • the object of the invention was also to demonstrate a method for producing such sources.
  • radioactive ruthenium-106 radiation sources which comprise an activity carrier and an enclosure of the carrier made of a body-compatible material, a multi-layer system made of metals and / or alloys having at least two layers of radioactive ruthenium being applied to the carrier exist and between the radioactive ruthenium layers there are inactive intermediate layers of other metals or alloys.
  • These radiation sources according to the invention have well-adhering ruthenium layers of the necessary thickness (and thus the necessary dose rate), which despite the typical bending stress, for example in the case of intravascular treatment of vascular anomalies, optically crack-free.
  • the radiation sources according to the invention are produced by electrolytic deposition of this multilayer system on a conductive carrier.
  • a galvanic radioactive ruthenium bath For the galvanic radioactive ruthenium bath,
  • RuNC anionic ruthenium complex [Ru 2 NCl8 (H 2 0) 2 ]
  • PPS sulfopropylpyridine
  • the RuNC electrolyte is produced in one step by hydrolysis of ruthenium (III) chloride solution, which for the purposes of the invention contains at least 8 Ci / g ruthenium, in an excess of amidosulfonic acid. This production is essentially known from the literature. Under the present active conditions, refluxing is replaced by tempering to about 90 ° C.
  • the electrolyte thus obtained can be used without further steps, so that, according to the invention, the preparation of the electrolyte is carried out directly in the electrolysis cell developed for the method according to the invention (cf. FIG. 1).
  • Gold, nickel, titanium or their alloys can be deposited as metals between the individual ruthenium layers. It is also possible according to the invention not to produce all intermediate layers from the same metal, but to use different metals for the intermediate layers. If the activity carrier produced according to the invention is to be enclosed by means of an electrodeposable cover layer, gold is preferably used here. In a preferred embodiment, the intermediate layers are also made of gold, it being possible to use commercially available galvanic gold baths from Degussa.
  • the “Auruna® 311” electrolyte for the first gold layer on the carrier which serves as an adhesion promoter between the carrier and the first ruthenium layer, and the “Auruna®” electrolyte for the intermediate layers 533 ". If the radiation source is to be enclosed by means of an electrodeposited cover layer, the Auruna® "533" electrolyte is also suitable for producing a hard gold layer.
  • supports made of brass, copper, alloyed steels, nickel, titanium or their alloys, silver, gold or platinum metals are suitable as metallic supports which also serve as cathode.
  • Nitinol or gold are preferably used as the carrier material.
  • surface-modified, ie, electrically conductive, polymers as supports.
  • the carrier can have any shape or form. It can also consist of several support elements, each of which has the multilayer system. A tube or several tubular elements, a single wire or an arrangement of several wires, a structured or unstructured film, a net, a rotationally symmetrical shaped body or a sphere can be used as the carrier. A wire or tube is preferably used.
  • tubular elements with a circular cross section which can particularly preferably consist of gold, are used as supports, the outer diameter of which is larger at each end than in intermediate section (see FIG. 2a).
  • the outer diameter of the tubular elements is up to 0.6 mm at the ends and up to 0.3 mm in the intermediate section.
  • the length of the elements is 0.5-70 mm, depending on the desired application and the necessary flexibility.
  • these tubular elements “threaded onto the wire” form the 106 Ru radiation source (cf. FIG. 3). Because the individual elements can be freely rotated, this radiation source is particularly flexible.
  • the pretreatment of the carrier used is of essential importance for the adhesive strength of the multilayer coating according to the invention. This must be degreased and any oxide layers and any adhering particles must be removed. If nitinol is used as a carrier, a final pickling with a mixture of hydrofluoric acid and hydrochloric acid has proven to be advantageous. In a preferred embodiment, a gold layer is applied as an adhesion promoter to the carrier made of nitinol as the first layer.
  • pre-gilding can of course be omitted. If tubular elements - as described above - are to be coated, the sections to be left free must be coated at the ends with a masking varnish.
  • the electrolytic deposition of the ruthenium layers according to the invention takes place in compliance with the following operating parameters:
  • the ruthenium concentration at the beginning of the electrolysis is typically 5 g / 1 and can drop to 0.2 g / 1 due to depletion of ruthenium.
  • the temperature should be between 60-75 ° C, preferably 70 ° C, the pH must be kept between 1.3-1.8.
  • the ruthenium concentration and the pH value are checked and adjusted at regular intervals.
  • ruthenium-106 radiation sources are thus provided which have sufficiently thick, well-adhering, crack-free, homogeneous and flexible radioactive ruthenium layers.
  • radioactive ruthenium layers with a thickness of up to 5 ⁇ m are achieved.
  • ruthenium-106 total layer thicknesses of up to 30 ⁇ m are achieved, whereby as Total layer thickness is understood as the sum of all radioactive ruthenium layers.
  • the ruthenium radiation sources produced from these multi-coated ruthenium activity carriers have a dose rate of at least 1.5 to 15 Gy per min at a distance of 2 mm (in water).
  • the electrolysis cell preferably used according to the invention consists of a vessel 1 with a double jacket 7 for temperature control.
  • the dimensions of the electrolysis vessel 1 must meet the requirement for a minimum working volume.
  • the working volume should preferably not exceed 5 ml.
  • the electrolysis vessel 1 must be suitable for the preparation and adjustment of the electrolyte in such a way that the addition of liquids via an opening 10 and stirring of the electrolyte by means of a stirrer 5 is possible.
  • the cathode 2 must also be able to be positioned in the electrolyte in accordance with the desired active length.
  • the electrolytic cell 1 was designed in such a way that the cathode 2 is connected to a device for opening the working space 3.
  • the anode 4 coaxially surrounds the cathode 2.
  • the electrolysis vessel 1 contains an element for the extraction of gases and vapors 6, so that a slight negative pressure can be permanently applied.
  • FIG. 2 shows the tubular support elements used in a preferred embodiment, a) without and b) with a coating.
  • Fig. 3 shows the coated on a wire "tubular" coated tubular elements in their
  • Example 1 Electrolytic generation of radioactive ruthenium layers by using nitinol wire with a diameter of 0.3-0.5 mm and the intermediate layers and the cover layer being made of gold.
  • Pre-gilding serves to promote adhesion between the substrate and the Ru layer.
  • the commercial electrolyte Auruna® 311 was chosen as gold. A previous acid activation is already given by the pickling. Gold is also suitable as an intermediate layer between the Ru deposits, with the electrolyte Auruna® 533 being selected.
  • the preactivation is carried out by pickling with sulfuric acid (5%, RT, 0.5 min). Both electrolytes are cyano-gold complexes from Degussa. 12
  • Auruna® 533 (Degussa, 8 g / 1, 35 ° C, 7 mm, 1 A / dm 2 )
  • the Ru complex RuNC is used as an electrolyte.
  • the preparation takes place in advance directly in the specially developed electrolysis cell.
  • the electrolyte was modified by adding PPS (sulfopropyl pyrid, 3 g / 1, from Raschig).
  • the operating parameters of Ru electrolysis are: -Ru concentration range 4.8-0.2 g / 1 Ru
  • this can also be made of hard gold (analogous to the intermediate layers using Auruna® 533).
  • Radioactive ruthenium radiation source by electrolytic production of radioactive ruthenium layers on a conductive support, by coating a nitinol tube or wire with an outer diameter of 0.2-0.6 mm over a length of 0.5-7 cm and intermediate layers as well the gold top layer can be used. 13
  • the quality parameters of the top layer must guarantee freedom from pores against the washing out of radioactive soot and freedom from cracks under typical mechanical stress and wear resistance against abrasion on HD-PE.
  • Such a cover layer can be produced from hard gold (see example 1).
  • the elements are made of gold and can only be coated with ruthenium on the thin, intermediate sections. This object is achieved in that sections to be left free are covered with a non-conductive masking lacquer.
  • the carriers are pretreated as described in Example 1, with the omission of step 4.
  • Example. 1 The cover layer is applied as described in Example 1. Since the cover layer is to be applied to the masked Rohrab ⁇ cuts, of these, the masking lacquer by dissolving in acetone is removed.
  • the tubular members thus produced unit length ⁇ Licher be pushed onto a wire and secured at the ends against falling out (for example by welding an end piece).
  • Pipe-like parts with different outer diameters in sections are used as carriers
  • the elements are made of gold or titanium and can only be coated with ruthenium on the thin, intermediate sections. This object is achieved in that sections to be left free with a non-conductive
  • the carriers are pretreated as described in Example 1.
  • the ruthenium deposition is carried out as in Example 1.
  • the Maskie ⁇ approximately lacquer by dissolving in acetone is removed.
  • the gold top layer is not applied. Instead, the tubular parts are inserted into a larger tube of the same material.
  • the uncoated edge of the carrier activity ⁇ (outer diameter 0.28 mm) is welded tubes with the closure at the ends.
  • the now encapsulated tubular elements of uniform length are pushed onto a wire and fixed at both ends.
  • different numbers of bodies can be threaded.
  • the individual free rotatability of the individual bodies provides flexibility in the overall arrangement.
  • the encapsulation of the individual bodies provides increased stability and, in particular, greater abrasion resistance.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electroplating And Plating Baths Therefor (AREA)

Abstract

L'invention concerne des sources irradiantes radioactives au ruthénium d'un débit de dose d'au moins 1,5 Gy/min à 2 mm de distance (eau), comprenant un support d'activité et un encapsulage du support en une matière compatible avec le corps humain. Un système multicouche de métaux et/ou d'alliages est appliqué galvaniquement sur le support, système dans lequel au moins deux couches sont constituées par du ruthénium 106, et des couches intermédiaires inactives d'autres métaux ou alliages sont prévues entre les couches de ruthénium radioactives. Le support d'activité est encapsulé par une matière, par exemple métal ou matière plastique, compatible avec le corps humain. L'encapsulage du support d'activité peut s'effectuer par remplissage dans une capsule suivi de sa fermeture, ou par dépôt galvanique d'une couche de recouvrement, par exemple en or dur.
EP99916898A 1998-03-31 1999-03-30 Sources irradiantes radioactives au ruthenium a debit de dose eleve, a usage medical et leur procede d'obtention Withdrawn EP0986818A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19815568 1998-03-31
DE19815568A DE19815568C2 (de) 1998-03-31 1998-03-31 Verfahren zur Herstellung von medizinischen radioaktiven Ruthenium-Strahlenquellen durch elektrolytische Abscheidung von radioaktivem Ruthenium auf einem Träger, mit diesem Verfahren hergestellte Strahlenquellen und Elektrolysezelle zur Erzeugung von radioaktiven Ruthenium-Schichten
PCT/EP1999/002159 WO1999050855A1 (fr) 1998-03-31 1999-03-30 Sources irradiantes radioactives au ruthenium a debit de dose eleve, a usage medical et leur procede d'obtention

Publications (1)

Publication Number Publication Date
EP0986818A1 true EP0986818A1 (fr) 2000-03-22

Family

ID=7863879

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99916898A Withdrawn EP0986818A1 (fr) 1998-03-31 1999-03-30 Sources irradiantes radioactives au ruthenium a debit de dose eleve, a usage medical et leur procede d'obtention

Country Status (5)

Country Link
US (1) US6319190B1 (fr)
EP (1) EP0986818A1 (fr)
JP (1) JP2002500772A (fr)
DE (1) DE19815568C2 (fr)
WO (1) WO1999050855A1 (fr)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6471671B1 (en) 2000-08-23 2002-10-29 Scimed Life Systems, Inc. Preloaded gas inflation device for balloon catheter
US6416492B1 (en) 2000-09-28 2002-07-09 Scimed Life Systems, Inc. Radiation delivery system utilizing intravascular ultrasound
US7776310B2 (en) 2000-11-16 2010-08-17 Microspherix Llc Flexible and/or elastic brachytherapy seed or strand
US7060020B2 (en) * 2001-11-02 2006-06-13 Ideamatrix, Inc. Delivery system and method for interstitial radiation therapy
US7074291B2 (en) 2001-11-02 2006-07-11 Worldwide Medical Technologies, L.L.C. Delivery system and method for interstitial radiation therapy using strands constructed with extruded strand housings
US7070554B2 (en) 2003-01-15 2006-07-04 Theragenics Corporation Brachytherapy devices and methods of using them
US6997862B2 (en) 2003-05-13 2006-02-14 Ideamatrix, Inc. Delivery system and method for interstitial radiation therapy using seed strands with custom end spacing
US8187159B2 (en) 2005-07-22 2012-05-29 Biocompatibles, UK Therapeutic member including a rail used in brachytherapy and other radiation therapy
US7736293B2 (en) 2005-07-22 2010-06-15 Biocompatibles Uk Limited Implants for use in brachytherapy and other radiation therapy that resist migration and rotation
US7988611B2 (en) 2006-05-09 2011-08-02 Biocompatibles Uk Limited After-loader for positioning implants for needle delivery in brachytherapy and other radiation therapy
US7874976B1 (en) 2006-09-07 2011-01-25 Biocompatibles Uk Limited Echogenic strands and spacers therein
US7878964B1 (en) 2006-09-07 2011-02-01 Biocompatibles Uk Limited Echogenic spacers and strands
KR101409458B1 (ko) * 2007-11-28 2014-06-19 삼성전자주식회사 방향 기능을 갖는 휴대용 단말기 및 이를 구비한 단말기충전 장치
CN108780680B (zh) 2016-03-31 2020-11-13 株式会社自动网络技术研究所 通信用电线

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DE901685C (de) * 1947-09-27 1954-01-14 United States Radium Corp Radioaktive Matallfolie
FR1206612A (fr) * 1956-01-23 1960-02-10 Centre Nat Rech Scient Procédé de préparation de dépôts et de revêtements de ruthénium métallique par électrolyse
GB1407592A (en) * 1971-12-17 1975-09-24 Int Nickel Ltd Electrodeposition of ruthenium
GB1520140A (en) * 1976-06-08 1978-08-02 Inco Europ Ltd Electrodeposition of ruthenium
US4297178A (en) * 1979-04-10 1981-10-27 The International Nickel Company, Inc. Ruthenium electroplating and baths and compositions therefor

Non-Patent Citations (1)

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Title
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Also Published As

Publication number Publication date
DE19815568C2 (de) 2000-06-08
DE19815568A1 (de) 1999-10-07
US6319190B1 (en) 2001-11-20
WO1999050855A1 (fr) 1999-10-07
JP2002500772A (ja) 2002-01-08

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