US3832457A - Ferrite contrast media with metallic oxides - Google Patents

Ferrite contrast media with metallic oxides Download PDF

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US3832457A
US3832457A US00046913A US4691370A US3832457A US 3832457 A US3832457 A US 3832457A US 00046913 A US00046913 A US 00046913A US 4691370 A US4691370 A US 4691370A US 3832457 A US3832457 A US 3832457A
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ferrite
weight
percent
oxide
contrast media
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M Sugimoto
K Funaki
Y Saeki
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RIKEN Institute of Physical and Chemical Research
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RIKEN Institute of Physical and Chemical Research
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Priority claimed from JP44048724A external-priority patent/JPS4829123B1/ja
Priority claimed from JP44048725A external-priority patent/JPS4829124B1/ja
Priority claimed from JP44091718A external-priority patent/JPS4829126B1/ja
Priority claimed from JP45040656A external-priority patent/JPS4946055B1/ja
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00—Preparations for testing in vivo
    • A61K49/04—X-ray contrast preparations
    • A61K49/0409—Physical forms of mixtures of two different X-ray contrast-enhancing agents, containing at least one X-ray contrast-enhancing agent which is not a halogenated organic compound
    • A61K49/0414—Particles, beads, capsules or spheres
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K49/00—Preparations for testing in vivo
    • A61K49/04—X-ray contrast preparations
    • A61K49/0409—Physical forms of mixtures of two different X-ray contrast-enhancing agents, containing at least one X-ray contrast-enhancing agent which is not a halogenated organic compound
    • A61K49/0414—Particles, beads, capsules or spheres
    • A61K49/0423—Nanoparticles, nanobeads, nanospheres, nanocapsules, i.e. having a size or diameter smaller than 1 micrometer
    • A61K49/0428—Surface-modified nanoparticles, e.g. immuno-nanoparticles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y5/00—Nanobiotechnology or nanomedicine, e.g. protein engineering or drug delivery
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/01—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials
    • H01F1/03—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity
    • H01F1/12—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials
    • H01F1/34—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites
    • H01F1/36—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles
    • H01F1/37—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of inorganic materials characterised by their coercivity of soft-magnetic materials non-metallic substances, e.g. ferrites in the form of particles in a bonding agent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01F—MAGNETS; INDUCTANCES; TRANSFORMERS; SELECTION OF MATERIALS FOR THEIR MAGNETIC PROPERTIES
    • H01F1/00—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties
    • H01F1/44—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids
    • H01F1/445—Magnets or magnetic bodies characterised by the magnetic materials therefor; Selection of materials for their magnetic properties of magnetic liquids, e.g. ferrofluids the magnetic component being a compound, e.g. Fe3O4

Definitions

  • barium sulfate has been used for X-ray examination of the esophagus and gastrointestinal tract.
  • Barium sulfate, with a strong X-ray absorbing power deposits in relatively large amounts on affected parts and gives X-ray pictures with sufficient contrast for detection of new seats of diseases or for diagnosis of the conditions. Difficulties are involved, however, in causing deposition of a desired amount of the contrast medium on a particular part desired.
  • a high degree of clinical skill is needed today in detecting a small affected part or in exactly diagnosing a disease condition.
  • FIG. 1 is a graph showing the amounts of various soft magnetic ferrite powders dissolved in an artificial gastric juice
  • FIG. 2 is a graph illustrating the relationship between the firing temperatures and the amounts of ferrites made of Fe O in the form of either coarse particles or finely divided particles dissolved in an artificial gastric uice;
  • FIG. 3 is a graphic representation of measurements of the minimum field strengths necessary for free movement of various soft magnetic ferrite powders in liquid, or the minimum field strengths necessary for maintaining such powders in certain positions in the liquid;
  • FIG. 4 is a schematic perspective view of an instrument for determining the 'X-ray absorbing powers of contrast media
  • FIG. 5 is a graph showing changes in saturation magnetization with the addition of BaO to a Ni-Zn ferrite, W0 to a Mn-Zn ferrite, and Ce O to a Cu-Zn ferrite;
  • FIG. 6 is a graph giving the results of comparative measurements of the relationship between the voltage applied on the X-ray tube and the X-ray absorbing power of barium sulfate contrast medium and a contrast medium prepared by adding BaO to a Mn-Zn ferrite.
  • the curve 1 represents a Cu-Zn ferrite powder (with a composition of a molar ratio of 25 CuO 25 ZnO 50 Fe O fired in air at 950C for 5 hours)
  • the curve 2 shows a powder of the solid solution of MgFe O and MgO (with the composition proposed by Frei, Gunders et al., fired in air at l,300C for 5 hours)
  • the curve 3 shows a Ni-Zn ferrite powder with a composition of a molar ratio of 25 NiO 25 ZnO 50 Fe O fired in air at l,300C for 5 hours)
  • the curve 4 shows a Mn-Zn ferrite powder (composed at a molar ratio of 25 MnO 25 ZnO 50 Fe O and fired in air at a
  • the curve 6 represents 'y-Fe O obtained by heating the Fe O powder of the curve 5 in air at 200C for 24 hours.
  • the starting materials used for the preparation of these ferrites were carbonates and oxides as commercially available special-grade reagents. The materials were thoroughly mixed and each mixture was heated. After cooling, the mixture was ground well in an agate mortar to a particle size of 0.1 to 0.2 micron in diameter. Ten gram of each ferrite powder were placed in 200 cc. of an artificial gastric juice or intestinal juice for from 30 minutes to 3 hours, and the filtrates were chemically analyzed and the amounts of the ferrite dissolved were estimated. From FIG.
  • the artificial gastric juice was prepared in conformity with the Japanese Pharmacopoeia by diluting a mixture of 2.0 g sodium chloride, 3.2 g pepsin, and 24.0 ml dilute hydrochloric acid with distilled water to a total volume of 1,000 ml.
  • the artificial intestinal juice was prepared of 15.0 g sodium hydrogen carbonate and 2.8 g pancreatin diluted altogether with purified water to a total volume of 1,000 ml.
  • a Ni-Zn ferrite is formed by introducing a mixed aqueous solution of nickel sulfate, zinc sulfate, and ferric sulfate in an aqueous solution of caustic soda and thereby coprecipitating the Ni-Zn ferrite salt
  • Ni-Zn, and Mn-Zn ferrites were produced Cu- Zn, Ni-Zn, and Mn-Zn ferrites, and then those ferrites were placed in the artificial gastric juice to determine the amounts dissolved.
  • the solubility of the ferrites formed by the coprecipitation technique ' was five to six times as much as the Cu-Zn ferrite in FIG. 1.
  • the ferrites obtained by the alkali coprecipitation when boiled in distilled water at lOfor many hours, showed a common tendency of decreasing solubility to the artificial gastric juice. Also, the coprecipitated ferrites upon treatment with boiling water in an autoclave exhibited remarkable decreases in the amounts dissolved in the artificial gastric juice. It was observed that, when heated to about 600C, the various ferrites obtained by the coprecipitation show almost the same rates of dissolution as in FIG. 1.
  • FIG. 2 illustrates the effect of particle size of the material a-Fe O upon the solubility of the product Mn-Zn ferrite.
  • the curve 7 represents the relationship between the firing temperature and the amount of dissolution in the artificial gastric juice for Mn-Zn ferrite (with a composition of a molar ratio of 30 MnO 20 ZnO O Fe O made of coarse-particle a-Fe O (0.2 micron in diameter).
  • the curve 8 represents the similar relationship for Mn-Zn ferrite made of an a-Fe O with high purity and fine particle size (0.05 micron in diameter) prepared by decomposing iron chloride in an oxygen atmosphere. Ferrites made of the fine-particle material, even if fired at a low temperature, showed a small solubility.
  • the firing temperature only has to be increased in order to reduce the amount of a ferrite that is dissolved in the artificial gastric juice.
  • FIG. 2 indicates that the heating at a temperature of at least 1,000C is preferable and that, when fired at 1,300C or upwards, the solubility of ferrite is saturated.
  • An elevated firing temperature would make the ferrite so dense and tight that grounding of fired ferrites into finely divided powder is rendered difficult. For these reasons, it is important for the manufacture of a ferrite contrast medium to fire the raw material mixture at a lowest possible temperature without fabricating it to any shape.
  • ferrite contrast media completely inert to the artificial gastric juice is to immerse a given ferrite powder in an acidic solution, e.g., an aqueous solution of hydrochloric acid, with a pH of about 1.0 for many hours, and then thoroughly wash the powder with distilled water.
  • an acidic solution e.g., an aqueous solution of hydrochloric acid
  • ferrite powders were placed each in 10 to times by weight of an aqueous solution of hydrochloric acid with a pH of about 1.0, agitated continuously for 5 to 10 hours, and filtered. Each filtrate was washed several times with distilled water and then dried.
  • the ferrite contrast media obtained in this way were placed in the artificial gastric juice for 3 hours.
  • the minimum magnetic field strengths required for moving the ferrite particles in dispersions of various ferrites in distilled water and also the minimum field strengths required for holding the ferrite particles in certain positions in the liquid were determined.
  • the results, graphically shown in FIG. 3, are those of experiments with ferrites having two different particle size, i.e., 0.4 micron and 0.2 micron in diameter. Particle size being equal, the Mn-Zn ferrite would be able to be freely moved or held at a place by the smallest magnetic field.
  • the minimum field-strength necessary for moving the ferrite particles 0.05 micron in diameter, was 35 oersteds.
  • a contrast medium of soft ferrite for radio-therapy is moved by the magnetic field correspond to saturation magnetization among the magnetic characteristics of the ferrite.
  • ferrite powder of an excessively large particle size When dispersed in liquid, a ferrite powder of an excessively large particle size will immediately settle down. Experiment disclosed that the particles should be not more than 0.2 micron in diameter. A ferrite powder 0.2 micron in diameter upon dispersion in distilled water settled down in about 2 to 3 minutes, whereas a 0.01-micron ferrite powder took about 50 minutes for the complete settling. Thus ferrites, when dispersed in liquid, tend to separate from the liquid and settle down within relatively short periods of time.
  • any such additive is much in excess of the percentage proportion above given, it increases the viscosity of the suspension to such an extent that the ferrite powder is no longer moved by the action of a magnetic field applied from the outside. It is therefore desirable to limit the proportion of such an addition agent, that is, starch to not more than 2 percent by weight of the total weight of the liquid, sodium alginate to not more than 0.3 percent by weight, or polyvinyl alcohol to not more than 6 percent by weight.
  • the three addition agents displayed sufficient high degrees of dispersibility.
  • the soft magnetic ferrite powders having particle sizes of 0.2 micron or less in diameter can be kept uniformly dispersed for many hours in the liquid by the addition of one or more members of the addition agent family consisting of starch, sodium alginate and polyvinyl alcohol.
  • the liquid in which the ferrite powders are to be dispersed is not limited to distilled water, but, for example, a carcinostatic liquid may be employed as well. In v the latter case, it is possible to mix a ferrite powder in an anti-cancer liquid medicine and, after oral administration of the liquid dispersion, keep the medicine in contact with the malignantly affected part for many hours by taking advantage of the magnetism of the ferrite.
  • An optimum mixing ratio of a ferrite powder as a contrast medium that utilizes a magnetic field to a liquid is, on the weight basis, 30 to 50 of the ferrite powder to 70 to 50 of the liquid.
  • the ferrite contrast media of this invention when administered to mice, showed no toxicity.
  • a contrast medium for use in radiotherapy is a sufficiently great X-ray absorbing power.
  • X-ray absorption factor of a dispersion of barium sulfate in distilled water (in 50 wt. percent concentration) which immersed in a row and held upright in the center of a water tank as shown in FIG. 4, at a distance of 5 centimeters each from the front and rear panels of the tank, the space in between being filled with water, and then the X-ray absorption factors were determined.
  • the voltage applied to the X-ray tube was 60 kilovolts.
  • the addition of the oxides referred to above increases the X-ray absorption factors of the ferrite contrast media of this invention to oxide to the ferrite.
  • any such oxide is to be added, it should be added in an amount of to 20 percent by weight of the total weight of the ferrite.
  • the increase in the amount of such an oxide to be added will raise the X-ray absorption factor but, on the other hand, lower the magnetism of the particular ferrite. This is exemplified in FIG.
  • the curve 9 represents the Ni-Zn ferrite with BaO added
  • the curve 10 the Mn-Zn ferrite with W0 added
  • the curve 11 the Cu-Zn ferrite with Ce O added.
  • the addition of the oxide causes a substantially linear decline of the intensity of saturation magnetization of the specific ferrite (as determined with 7,000 oersteds). Accordingly, if the magnetism is lowered by the excessive addition of the oxide, the ferrite powder will become hardly movable upon the application of a magnetic field.
  • the addition of the oxide in an amount between 5 and percent by weight is most beneficial.
  • the above range is chosen on the ground that, if the amount of the oxide to be added is less than 5 percent by weight, the increment of the X-ray absorption factor thereby attained is too little and, if the amount is in excess of 20 percent by weight, the magnetism is badly affected although the X-ray absorption factor is considerably increased.
  • the oxide to be added may be premixed with the ferrite material and fired together.
  • the mixture may be easily prepared by adding the oxide to a liquid mixture or a solution of the ferrite material in the liquid.
  • the X-ray absorption factor of a contrast medium depends upon the voltage to be applied to the X-ray tube. Therefore, it is important that the ferrite contrast medium obtained by the addition of the oxide should be capable of use over a wide range of the applied voltage for the X-ray tube.
  • the curve 12 represents measured values of an ordinary contrast medium of barium sulfate
  • the curve 13 represents the measured values of the ferrite contrast medium of Mn Zn Fe O with BaO added. It is obvious that the contrast media of the BaO-containing ferrite and barium sulfate exhibit properties of the same tendency with changes of the voltage applied to the X-ray tube. Thus, the ferrite contrast media were also found useful over a wide range of applied voltage for the X-ray tube.
  • this invention concerns the method of producing ferrite contrast media for radiophotography characterized by the addition of one or more of the group of oxides consisting of Ba, Bi, Ce and W to one or more soft magnetic ferrites having a particle size of not more than 0.2 micron in diameter (ac-.
  • Table 3 shows the results of experiments conducted with a Mn-Zn ferrite by adding different percentages of ZrO It will be clear fromTable 3 that the X-ray absorption factor rises with the increase of the amount of ZrO added and that the addition of over 15 percent by weight renders the factor of the ferrite almost equal to that of barium sulfate. However, the induction begins to decrease sharply as the proportion of the ZrO exceeds 12 percent by weight. Where Zr0 is to be added, therefore, an amount in the range of 3 to 12 percent by weight is preferable.
  • Table 4 shows the results of experiments with a Fe-Zn ferrite with the addition of different amounts of SnO
  • the Fe-Zn ferrite upon the addition of SnO attains an X-ray absorption factor substantially equal to that of barium sulfate. However, if the amount added exceeds 14%, the induction sharply drops.
  • the amount to be added is preferably within the range of 3 to 12 percent by weight.
  • the X-ray absorption factor of the ferrite medium increases with the growing proportion of the addition agent, up to the point of percent by weight or more of the proportion where the ferrite exhibits an X-ray absorption substantially equal to that of barium sulfate.
  • the effective range of addition is between 3 and 12 percent by weight.
  • Table 7 X-ray absorp- Induction at Type of contrast medium tion factor I00 Oe. (gauss) Barium sulfate I00 0 o.ll o.4 z -l plus l0 wt.% La o 98 3200 do. Pr Q, 99 3300 do. Nd O; 99 3250 do. sm,0,, I00 3 I00 do. Eu Q, I00 3200 do. Cid- 0 3350 do. Th,0 95 3400 do. Dy Q, 96 3550 do. H0 0 96 3600 do. Yb O; 97 3400 sorption factors were measured with an anode voltage of 55 kilovolts.
  • the addition of the various oxides help the ferrite contrast media of the invention attain X-ray absorption factors close to that of barium sulfate.
  • X-ray powder tests indicated that those oxides will scarcely form solid solutions with the ferrites upon firing at elevated temperatures.
  • These oxides may be added in a suitable way, for example, in such a manner that the divalent metallic ions of the particular oxide to be added substitute for the divalent metallic ions of the ferrite or that the trivalent metallic ions of the oxide substitute for the Fe of the ferrite.
  • such an oxide may be simply added to the ferrite. When any such oxide is to be added to a given ferrite, the amount should be in the range of 3 to 12 percent by weight of the total weight of the ferrite.
  • the oxide to be added may be premixed with the ferrite material and baked together.
  • an oxide-containing ferrite may be easily prepared by mixing the ferrite material with the liquid and then adding the oxide to the resulting mixed solution.
  • any such oxide is to be added to a coprecipitated ferrite, it is possible to dissolve the chloride, sulfate or nitrate of the metallic ions of such an oxide in water, and then effect the coprecipitation with the ferrite in alkali, or add a necessary amount of a carbonate or oxalate to the coprecipitated ferrite and then heat the mixture at 400 to 600C for many hours.
  • mice when administered to mice, showed no toxicity.
  • a total of 30 mice were dosed with those ferrites at the rate of 1 gram per mouse per day for a period of about 2 months, and the dose did not prove lethal to any animal tested.
  • the present invention pertains to a method of producing ferrite contrast media which comprises adding one or more members of the class of oxides consisting of Zr, Sn, Ta, Y, La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho and Yb, in an amount of about- 3 to 12 percent by weight, to one or more soft magnetic ferrites having a particle size of not more than 0.2 micron (in a mixture with a liquid at the ratio of 10 to 65 percent by weight to the balance liquid).
  • the use of the contrast media according to the invention makes it possible with ease to pinpoint any Table 8 Ferrite 40 (g) Water 54.22 Sodium alginate 0.25 Polyvinyl alcohol 5.5 Tragacanth rubber 0.02 Peppermint oil 0.01
  • a diagnostic X-ray apparatus provided with a magnetic device was developed to examine whether the ferrite contrast media could be carried easily to an organ to be examined and held for a long period.
  • This apparatus comprises a conventional diagonostic X-ray apparatus and two kinds of electromagnets and a means to displace said electromagnets. More particularly, it consists of two electromagnets of 1,500 and 2,000 oersted respectively, and the device to displace these electromagnets verticularly and in horizontal plane.
  • a magnetic field for example, about 350 oersted is applied, the ferrite contrast media can be displaced or fixed to any desired position.
  • the imitation model for the gullet and gastrointestine duct were tested utilizing the above described ferrite contrast media and diagnostic X-ray apparatus.
  • the imitation model for the human gullet and gastrointestine duct was used for observation of capability for the controlling locations of the ferrite contrast media.
  • the obtained result revealed to be so excellent that is proved for the sufficient availability in the examination of the gullet and gastrointestine duct.
  • test animals such as mice, rats, hares and dogs were administered with the ferrite contrast media and examined with said newly developed X-ray apparatus to serve for the fundamentalexperiments for the application to the diagnosis.
  • the ferrite contrast media according to the present invention could be maintained at the desired location of gullet and gastrointestine duct for a long period and displaced from one location to others or examined repeatedly at the same location. Inasmuch as an ample prospect has been obtained for the X-ray inspection of the gullet and gastrointestine duct for a satisfactory and sufficient period, it is suggested that an earlier detection of cancer occuring in the gullet and gastrointestine duct will be more practical than before.
  • a mass of ferrite contrast medium is settled in the upper gullet by the effect of a magnetic field and is gradually displaced toward the stomach so that the gullet may be inspected more accurately and easily.
  • the retained period of the medium in the stomach is easily controllable due to the magnetic field.
  • a radiographic contrast medium comprising an aqueous dispersion of a. from about 10 to about 65 percent by weight
  • At least one magnetic ferrite having a particle size of less than 0.2 l and 2. at least one metal oxide selected from the group consisting of i. from about 5 to about 20%, by weight of the ferrite, of an oxide of barium, bismuth, cerium or tungsten and ii. from about 3 to about 12 percent, by weight of the ferrite, of an oxide of zirconium, tin, tantalum, yttrium, lanthanum, praseodymium, neodymium, Samarium, europium, gadolinium, terbium, dysprosium, holmium or ytterbium, and
  • At least one dispersion agent selected from the group consisting of starch in an amount of from 1.0 to 2.0 percent by weight, based on the total weight of said aqueous dispersion, sodium alginate in an amount of from 0.1 to 0.3 percent by weight, based on the total weight of said aqueous dispersion and polyvinyl alcohol in an amount of from 4 to 6 percent by weight, based on the total weight of said aqueous dispersion.
  • a radiographic contrast medium according to claim 1 wherein the magnetic ferrite is selected from the group consisting of copper-zinc ferrite, magnesium ferrite, nickel-zinc ferrite, manganese-zinc ferrite, ferrosoferric oxide, iron-zinc ferrite, and ferric oxide.

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JP44048724A JPS4829123B1 (fr) 1969-06-20 1969-06-20
JP44048725A JPS4829124B1 (fr) 1969-06-20 1969-06-20
JP44091718A JPS4829126B1 (fr) 1969-11-15 1969-11-15
JP45040656A JPS4946055B1 (fr) 1970-05-13 1970-05-13

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Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310507A (en) * 1978-08-02 1982-01-12 Eastman Kodak Company Contrast agent for radiography
WO1984004888A1 (fr) * 1983-06-09 1984-12-20 Field Group Chemicals Milieu opaque aux rayonnements
US4719098A (en) * 1983-05-04 1988-01-12 Schering Aktiengesellschaft Enteral contrast medium useful for nuclear magnetic resonance imaging and its preparation
US4731239A (en) * 1983-01-10 1988-03-15 Gordon Robert T Method for enhancing NMR imaging; and diagnostic use
US4770183A (en) * 1986-07-03 1988-09-13 Advanced Magnetics Incorporated Biologically degradable superparamagnetic particles for use as nuclear magnetic resonance imaging agents
US4957939A (en) * 1981-07-24 1990-09-18 Schering Aktiengesellschaft Sterile pharmaceutical compositions of gadolinium chelates useful enhancing NMR imaging
US5219552A (en) * 1986-04-07 1993-06-15 Francois Dietlin Compositions intended for use in tomo densitometry
US5417958A (en) * 1991-08-05 1995-05-23 Mallinckrodt Medical, Inc. Heavy metal clusters for use as imaging agents
US5618514A (en) * 1983-12-21 1997-04-08 Nycomed Imaging As Diagnostic and contrast agent
US5720939A (en) * 1985-08-15 1998-02-24 Nycomed Imaging As Method of contrast enhanced magnetic resonance imaging using magnetically responsive-particles
US5746999A (en) * 1984-11-23 1998-05-05 Schering Aktiengesellschaft Magnetic particles for diagnostic purposes
US20020136693A1 (en) * 1984-11-23 2002-09-26 Heinz Gries Magnetic particles for diagnostic purposes
US20050031543A1 (en) * 1992-01-09 2005-02-10 Amersham Health As Contrast agents
WO2005046733A1 (fr) * 2003-11-17 2005-05-26 Philips Intellectual Property & Standards Gmbh Agent de contraste pour des techniques d'imagerie medicale, et son utilisation
US20070003485A1 (en) * 1991-03-28 2007-01-04 Jo Klaveness Contrast agents
US20070255392A1 (en) * 2006-04-27 2007-11-01 Phillips Plastics Corporation Composite stent
US20080067467A1 (en) * 2004-08-02 2008-03-20 Sony Corporation Electromagnetism suppressing material, electromagnetism suppressing deveice, and electronic appliance

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2508802A1 (fr) * 1981-07-03 1983-01-07 Thomson Csf Procede d'hyperthermie medicale utilisant une poudre magnetique par voie sanguine, et dispositif de mise en oeuvre de ce procede

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US970215A (en) * 1910-06-29 1910-09-13 Oscar Gros Preparation impermeable for roentgen rays.
FR750173A (fr) * 1933-01-31 1933-08-05 Procédé pour la préparation de suspensions aqueuses de sulfate de baryum destinées aux examens aux rayons chi et moyens pour la mise en oeuvre dudit procédé
GB657979A (en) * 1948-07-03 1951-10-03 Miles Lab Improvements in or relating to x-ray contrast mediums
US3592185A (en) * 1967-04-18 1971-07-13 Yeda Res & Dev Ferromagnetic contrast media and method of use

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US970215A (en) * 1910-06-29 1910-09-13 Oscar Gros Preparation impermeable for roentgen rays.
FR750173A (fr) * 1933-01-31 1933-08-05 Procédé pour la préparation de suspensions aqueuses de sulfate de baryum destinées aux examens aux rayons chi et moyens pour la mise en oeuvre dudit procédé
GB657979A (en) * 1948-07-03 1951-10-03 Miles Lab Improvements in or relating to x-ray contrast mediums
US3592185A (en) * 1967-04-18 1971-07-13 Yeda Res & Dev Ferromagnetic contrast media and method of use

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
The Merck Index, 8th Ed., Merck & Co., Rahway, N. J., (1968), pp. 120 121. *

Cited By (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4310507A (en) * 1978-08-02 1982-01-12 Eastman Kodak Company Contrast agent for radiography
US4957939A (en) * 1981-07-24 1990-09-18 Schering Aktiengesellschaft Sterile pharmaceutical compositions of gadolinium chelates useful enhancing NMR imaging
US5021236A (en) * 1981-07-24 1991-06-04 Schering Aktiengesellschaft Method of enhancing NMR imaging using chelated paramagnetic ions bound to biomolecules
US4963344A (en) * 1981-07-24 1990-10-16 Schering Aktiengesellschaft Method to enhance NMR imaging using chelated paramagnetic ions
US4731239A (en) * 1983-01-10 1988-03-15 Gordon Robert T Method for enhancing NMR imaging; and diagnostic use
US4719098A (en) * 1983-05-04 1988-01-12 Schering Aktiengesellschaft Enteral contrast medium useful for nuclear magnetic resonance imaging and its preparation
WO1984004888A1 (fr) * 1983-06-09 1984-12-20 Field Group Chemicals Milieu opaque aux rayonnements
US6544496B1 (en) 1983-12-21 2003-04-08 Amersham Health As Diagnostic and contrast agent
US5817291A (en) * 1983-12-21 1998-10-06 Nycomed Imaging As Method of ultrasonic imaging comprising administering biocompatible spheres or particles
US5618514A (en) * 1983-12-21 1997-04-08 Nycomed Imaging As Diagnostic and contrast agent
US5670135A (en) * 1983-12-21 1997-09-23 Nycomed Imaging As Ultrasonic contrast agent comprising carbohydrate particles
US5746999A (en) * 1984-11-23 1998-05-05 Schering Aktiengesellschaft Magnetic particles for diagnostic purposes
US20020136693A1 (en) * 1984-11-23 2002-09-26 Heinz Gries Magnetic particles for diagnostic purposes
US5720939A (en) * 1985-08-15 1998-02-24 Nycomed Imaging As Method of contrast enhanced magnetic resonance imaging using magnetically responsive-particles
US5219552A (en) * 1986-04-07 1993-06-15 Francois Dietlin Compositions intended for use in tomo densitometry
US4770183A (en) * 1986-07-03 1988-09-13 Advanced Magnetics Incorporated Biologically degradable superparamagnetic particles for use as nuclear magnetic resonance imaging agents
US20070003485A1 (en) * 1991-03-28 2007-01-04 Jo Klaveness Contrast agents
US5417958A (en) * 1991-08-05 1995-05-23 Mallinckrodt Medical, Inc. Heavy metal clusters for use as imaging agents
US20050031543A1 (en) * 1992-01-09 2005-02-10 Amersham Health As Contrast agents
US20050196342A1 (en) * 1992-01-09 2005-09-08 Jo Klaveness Contrast agents
WO2005046733A1 (fr) * 2003-11-17 2005-05-26 Philips Intellectual Property & Standards Gmbh Agent de contraste pour des techniques d'imagerie medicale, et son utilisation
US20080067467A1 (en) * 2004-08-02 2008-03-20 Sony Corporation Electromagnetism suppressing material, electromagnetism suppressing deveice, and electronic appliance
US7959821B2 (en) * 2004-08-02 2011-06-14 Sony Corporation Electromagnetism suppressing material, electromagnetism suppressing device, and electronic appliance
US20070255392A1 (en) * 2006-04-27 2007-11-01 Phillips Plastics Corporation Composite stent
US9155646B2 (en) * 2006-04-27 2015-10-13 Brs Holdings, Llc Composite stent with bioremovable ceramic flakes

Also Published As

Publication number Publication date
DE2030690C3 (de) 1974-06-12
FR2053000B1 (fr) 1974-08-30
FR2053000A1 (fr) 1971-04-16
DE2065532B2 (de) 1976-07-01
DE2065532A1 (de) 1974-05-16
DE2030690A1 (de) 1971-01-07
GB1315391A (en) 1973-05-02
DE2030690B2 (de) 1973-11-15

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