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Title:
STERILIZATION SYSTEM
Document Type and Number:
WIPO Patent Application WO/2018/153437
Kind Code:
A1
Abstract:
The present invention relates to a sterilization system (1) where the article (20) which is to be sterilized is coated with a Pr3+comprising material (10), which emits UV-C light upon stimulation with a blue LED (30).

Inventors:
JÜSTEL THOMAS (DE)
ESPINOZA VILLALBA SARA (DE)
MÜLLER MATTHIAS (DE)
ANDERSON R ROX (US)
PURSCHKE MARTIN (US)
Application Number:
PCT/EP2017/053960
Publication Date:
August 30, 2018
Filing Date:
February 21, 2017
Export Citation:
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Assignee:
FACHHOCHSCHULE MUENSTER (DE)
MASSACHUSETTS GEN HOSPITAL (US)
International Classes:
A61L2/10; G02F2/00; C09K11/77
Domestic Patent References:
WO2009064845A22009-05-22
Foreign References:
US20110171062A12011-07-14
Other References:
EZRA L. CATES ET AL: "Converting Visible Light into UVC: Microbial Inactivation by Pr 3+ -Activated Upconversion Materials", ENVIRONMENTAL SCIENCE & TECHNOLOGY, vol. 45, no. 8, 15 April 2011 (2011-04-15), US, pages 3680 - 3686, XP055410994, ISSN: 0013-936X, DOI: 10.1021/es200196c
Attorney, Agent or Firm:
MICHALSKI HÜTTERMANN & PARTNER PATENTANWÄLTE MBB (DE)
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Claims:
C l a i m s 1. Sterilization system for an article to be sterilized, whereby the surface of the article comprises at least partially a Pr3+ comprising material and/or a Pr3+ comprising material is provided so towards the article to be sterilized that the article is in the path of light emitted from the Pr3+ comprising material, furthermore comprising a light emitting device which emits light in the blue wavelength range towards the Pr3+ comprising material, so that the Pr3+ comprising material emits light with a lower peak wavelength than the incoming light from the light emitting device 2. Sterilisation sytem according to Claim 1, whereby the Pr3+ comprising material emits light in the UV wavelength range 3. Sterilization system according to claim 1 or 2, whereby the Pr3+ comprising material emits light in the UV-C wavelength range 4. Sterilization system according to any of the claims 1 or 3, whereby the article

comprises a coating which comprises the Pr3+ comprising material. 5. Sterilization system according to any of the claims 1 to 4, whereby the Pr3+ comprising material is selected from the group comprising: PrB03, PrPO4, PrOCl, PrOF, PrA103, Pr2Si207, Pr2Si05, Sr2Pr2Si4O13, PrMgAlnO19, PrMgB5O10, Pr2(SO4)3, PrMgAlnO19, Ca9Pr(PO4)7, YPO4:Pr3+, LaPO4:Pr3+, LuPO4:Pr3+, YB03:Pr3+, LuB03:Pr3+,

Y2Si05:Pr3+, Lu2Si05:Pr3+, Y2Si207:Pr3+, Lu2Si207:Pr3+, Sr(Al,Mg)i2O19:Pr3+, Ca2P207:Pr3+, YA103:Pr3+, LuA103:Pr3+, Li2SrSiO4:Pr3+, Li2CaSiO4:Pr3+,

Sr2Mg(B03)2:Pr3+, Lu706F9:Pr3+, NaYPO4F:Pr3+, YP309:Pr3+, LuP309:Pr3+,

KCaY(PO4)2:Pr3+, KCaLu(PO4)2:Pr3+, CaYAl307:Pr3+, CaLuAl307:Pr3+, YF3:Pr3+, LaF3:Pr3+, LuF3:Pr3+, YOF:Pr3+, YOCl:Pr3+, Ca9Y(PO4)7:Pr3+, Ca9Lu(PO4)7:Pr3+, Lu3(Al1-xGax)5O12:Pr, Y3(Al1-xGax)5O12:Pr, (Lu1_xYx)2Si207:Pr, (Lu1_xYx)2Si05:Pr, (Lu1-xYx)B03:Pr, (Lu1-xYx)A103:Pr, (Ca1-x-ySrxBay)5(PO4)3F:Pr,Na, (La1_

xGdx)MgAlnO19:Pr, (Lu1-xYx)PO4:Pr, LaPO4:Pr, Li(Lu1-xYx)F4:Pr, Na(Lu1-xYx)F4:Pr, K(Lu1-xYx)F4:Pr, Rb(Lu1-xYx)F4:Pr, Cs(Lu1-xYx)F4:Pr, (Ca1-x-ySrxBay)SO4:Pr,Na or mixtures thereof.

Description:
Sterilization System

D e s c r i p t i o n The present invention relates to sterilization system, especially sterilization system for clinical apparatuses.

Clinical systems and apparatuses, especially those who are applied to patients for a longer time, such as cannulas, hollow needles or syringes, require sterilization. However, many sterilization systems, especially those who use chemicals, have the drawback that they cannot be easily applied and sometimes might even endanger the patient.

Therefore there is a constant need for new and improved sterilization systems, especially for clinical apparatuses and it is a problem to provide such systems.

This problem is solved by a system according to Claim 1 of the present invention.

Accordingly a sterilization system for an to-be- sterlized article is provided whereby the surface of the article comprises at least partially a Pr 3+ comprising material and/or a Pr 3+ comprising material is provided so towards the article to be sterilized that the article is in the path of light emitted from the Pr comprising material, furthermore comprising a light emitting device which emits light in the blue wavelength range towards the Pr 3+ comprising material, so that the Pr 3+ comprising material emits light with a lower peak wavelength than the incoming light from the light emitting device.

By doing so it has surprisingly been found that an effective sterlization is possible without causing harm to the patient or at least reducing such harm to an absolute minimum.

The term "blue wavelength" especially means and/or includes a peak wavelength of > 430 to ≤ 460 nm.

For most applications within the present invention, at least one of the further advantages can be reached or observed:

Since the actual sterilization is achieved via the UV-C emittance of the Pr 3+ (known as a very effective sterilization tool) which is provided of the surface of the article itself or in vicinitiy thereof, but upon stimulation with blue light which is not harmful, the sterilization process is much less dangerous than existing solution where the UV-C light is used.

The process is continuous, as no chemical stock solutions etc. need to be refilled - The process is fast, since the UV-C radiation is generated at the point-of-use.

According to a preferred embodiment the Pr 3+ comprising material emits light in the UV wavelength range, preferably the UV-C wavelength range. This emittance occurs due to an upconversion process which is known to occur in many suitable Pr 3+ comprising materials.

The term "UV wavelength" especially means and/or includes a peak wavelength of≥ X to≤ Y nm, the term "UV-C wavelength" especially means and/or includes a peak wavelength of≥ X to≤ Y nm. According to a preferred embodiment of the present invention, the article that is to be sterilized comprises a coating which comprises the Pr 3+ comprising material. This has been found to be very effective for many applications within the present invention. The term coating especially means or includes that one or more outer surfaces of the article comprise a zone adjacent to the surface in whith the Pr 3+ concentration is higher than in the more remote areas of the article.

Especially if the article that is to be sterilized comprises or is glassware or has a polymer surface, it is especially preferred that the a coating can be applied onto the article according to one or more of the following techniques:

Dip coating

Doctor blade coating

- Spin coating

Slot die coating

Spray coating

For many applications, especially if the article comprises glassware, a thermal step may follow to increase the stability of the coating.

According to a preferred embodiment of the present invention, the Pr 3+ comprising material is selected from the group comprising: PrBOs, PrPO 4 , PrOCl, PrOF, PrA10 3 , Pr 2 Si 2 0 7 , Pr 2 Si0 5 , Sr 2 Pr 2 Si 4 O 13 , PrMgAlnO 19 , PrMgBsO 10 , Pr 2 (SO 4 ) 3 , PrMgAlnO 19 , Ca 9 Pr(PO 4 ) 7 , YPO 4 :Pr 3+ , LaPO 4 :Pr 3+ , LuPO 4 :Pr 3+ , YB0 3 :Pr 3+ , LuB0 3 :Pr 3+ , Y 2 Si0 5 :Pr 3+ , Lu 2 Si0 5 :Pr 3+ , Y 2 Si 2 0 7 :Pr 3+ , Lu 2 Si 2 0 7 :Pr 3+ , Sr(Al,Mg)i 2 O 19 :Pr 3+ , Ca 2 P 2 0 7 :Pr 3+ , YA10 3 :Pr 3+ , LuA10 3 :Pr 3+ , Li 2 SrSiO 4 :Pr 3+ , Li 2 CaSiO 4 :Pr 3+ , Sr 2 Mg(B0 3 ) 2 :Pr 3+ , Lu 7 0 6 F 9 :Pr 3+ , NaYPO 4 F:Pr 3+ , YP 3 0 9 :Pr 3+ , LuP 3 0 9 :Pr 3+ , KCaY(PO 4 ) 2 :Pr 3+ , KCaLu(PO 4 ) 2 :Pr 3+ , CaYAl 3 0 7 :Pr 3+ , CaLuAl 3 0 7 :Pr 3+ , YF 3 :Pr 3+ , LaF 3 :Pr 3+ , LuF 3 :Pr 3+ , YOF:Pr 3+ , YOCl:Pr 3+ , Ca 9 Y(PO 4 ) 7 :Pr 3+ , Ca 9 Lu(PO 4 ) 7 :Pr 3+ , Lu 3 (Ali- x Ga x ) 5 O 12 :Pr, Y3(Al 1-x Ga x ) 5 O 1 2:Pr, (Lu 1-x Yx) 2 Si 2 0 7 :Pr, (Lu 1-x Yx) 2 Si0 5 :Pr, (Lu 1 - x Yx)B0 3 :Pr, (Lu 1 _ xYx)A10 3 :Pr, (Ca 1-x - y SrxBa y ) 5 (PO 4 ) 3 F:Pr,Na, (La 1-x Gdx)MgAlnO 19 :Pr, (Lu 1-x Y x )PO 4 :Pr, LaPO 4 :Pr, Li(Lu 1 - x Yx)F 4 :Pr, Na(Lu 1 - x Yx)F 4 :Pr, K(Lu 1 - x Yx)F 4 :Pr, Rb(Lu 1 - x Yx)F 4 :Pr, Cs(Lu 1 _ x Yx)F 4 :Pr, (Ca 1-x -ySr x Ba y )SO 4 :Pr,Na, or mixtures thereof.

In case the article comprises or is made out of glassware, it is especially preferred that the Pr 3+ comprising material is selected from the group comprising PrB0 3 , PrPO 4 , PrOCl, PrOF, PrA10 3 , Pr 2 Si 2 0 7 , Pr 2 Si0 5 , Sr 2 Pr 2 Si 4 O 13 , PrMgAlnO 19 , PrMgBsO 10 , Pr 2 (SO 4 ) 3 , PrMgAlnO 19 , Ca 9 Pr(PO 4 ) 7 , YPO 4 :Pr 3+ , LaPO 4 :Pr 3+ , LuPO 4 :Pr 3+ , YB0 3 :Pr 3+ , LuB0 3 :Pr 3+ , Y 2 Si0 5 :Pr 3+ , Lu 2 Si0 5 :Pr 3+ , Y 2 Si 2 0 7 :Pr 3+ , Lu 2 Si 2 0 7 :Pr 3+ , Sr(Al,Mg)i 2 O 19 :Pr 3+ , Ca 2 P 2 0 7 :Pr 3+ , YA10 3 :Pr 3+ , LuA10 3 :Pr 3+ , Li 2 SrSiO 4 :Pr 3+ , Li 2 CaSiO 4 :Pr 3+ , Sr 2 Mg(B0 3 ) 2 :Pr 3+ , Lu 7 0 6 F 9 :Pr 3+ ,

NaYPO 4 F:Pr 3+ , YP 3 0 9 :Pr 3+ , LuP 3 0 9 :Pr 3+ , KCaY(PO 4 ) 2 :Pr 3+ , KCaLu(PO 4 ) 2 :Pr 3+ ,

CaYAl 3 0 7 :Pr 3+ , CaLuAl 3 0 7 :Pr 3+ , YF 3 :Pr 3+ , LaF 3 :Pr 3+ , LuF 3 :Pr 3+ , YOF:Pr 3+ , YOCl:Pr 3+ , Ca 9 Y(PO 4 ) 7 :Pr 3+ , Ca 9 Lu(PO 4 ) 7 :Pr 3+ or mixtures thereof, since these materials have proven themselves in many application to be easy applicable to glassware and in many applications be excellently compatible with glass, especially glass which is covered with or coated by metal oxides such as MgO, A1 2 0 3 , or MgAl 2 O 4 . This is the case for many apparatuses or articles used in medicinal or clinical applications because so the stickiness towards liquids can be reduced.

According to a preferred embodiment the light emitting device which emits light in the blue wavelength range is a blue LED, preferably with a peak of around 450 nm. This has proven itself in practice since these LED are widely available. According to a preferred embodiment, the light emitted from the light emitting device which emits light in the blue wavelength range is guided towards the article to be sterilized via a light guide. By doing so the article and the light emitting deviced can be separated which increases the flexibility of the sterilization system. The aforementioned components, as well as the claimed components and the components to be used in accordance with the invention in the described embodiments, are not subject to any special exceptions with respect to their size, shape, material selection and technical concept such that the selection criteria known in the pertinent field can be applied without limitations.

Additional details, characteristics and advantages of the object of the invention are disclosed in the subclaims and the following description of the respective figures—which in an exemplary fashion— show one preferred embodiment according to the invention. Such embodiment does not necessarily represent the full scope of the invention, however, and reference is made therefore to the claims and herein for interpreting the scope of the invention. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are intended to provide further explanation of the present invention as claimed. Fig. 1 shows a very schematic view of a sterilization system according to one embodiment of the present invention,

Fig. 2 shows the emission, excitation and reflection spectrum of an article to be sterilized according to one embodiment of the present invention,

Fig. 3 shows the emission, excitation and reflection spectrum of an article to be sterilized according to one embodiment of the present invention,

Fig. 4 shows the emission, excitation and reflection spectrum of an article to be sterilized according to one embodiment of the present invention,

Fig. 5 shows the emission, excitation and reflection spectrum of an article to be sterilized according to one embodiment of the present invention; and Fig. 6 shows the emission, excitation and reflection spectrum of a Pr comprising material which can be used for a sterilization system according to the present invention together with the Germicidal Action curve according to DIN 5031- 10. Fig. 1 shows a very schematic view of a sterilization system 1 according to one embodiment of the present invention. The system comprises an article 20 (in this case a glass syringe) which is coated on the inside with a Pr 3+ comprising material 10. The article 20 is coupled to a light guide 40, which itself is coupled to a LED 30. Upon stimulation with blue light from the LED 30, the coating 10 emits UV-C (indicated by the arrows) towards the liquid in the syringe, thereby sterilizing it.

Figs. 2 to 5 show spectra of several glass coated articles which can be used within the present invention. Fig. 2 shows the emission, excitation and reflection spectrum of a glass surface coated by Υ 0.98 Ρr 0.02 ΒO 3 . It can be seen that this article emits radiation at a peak wavelength of 270 nm upon excitation with 450 nm LEDs.

Fig. 3 shows the emission, excitation and reflection spectrum of a glass surface coated by PrMgAl 11 O 19 . It can be seen that this article emits radiation at a peak wavelength of 247 nm upon excitation with 450 nm LEDs.

Fig. 4 shows the emission, excitation and reflection spectrum of a glass surface coated by PrPO 4 . It can be seen that this article emits radiation at a peak wavelengh of 235 nm upon excitation with 450 nm LEDs.

Fig. 5 shows the emission, excitation and reflection spectrum of a glass surface coated by Li 2 CaSiO 4 :Pr(l%). It can be seen that this article emits radiation at a peak wavelengh of 247 nm upon excitation with 450 nm LEDs. Fig. 6 shows the emission spectrum of YB0 3 :Pr, which is another preferred material within the present invention together with the Germicidal Action curve according to DIN 5031-10. It can be seen that this material shows excellent sterilization properties.

The particular combinations of elements and features in the above detailed embodiments are exemplary only; the interchanging and substitution of these teachings with other teachings in this and the patents/applications incorporated by reference are also expressly contemplated. As those skilled in the art will recognize, variations, modifications, and other implementations of what is described herein can occur to those of ordinary skill in the art without departing from the spirit and the scope of the invention as claimed. Accordingly, the foregoing description is by way of example only and is not intended as limiting. In the claims, the word "comprising" does not exclude other elements or steps, and the indefinite article "a" or "an" does not exclude a plurality. The mere fact that certain measures are recited in mutually different dependent claims does not indicate that a combination of these measured cannot be used to advantage. The invention's scope is defined in the following claims and the equivalents thereto. Furthermore, reference signs used in the description and claims do not limit the scope of the invention as claimed.