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    • 专利摘要:
    Abstract The invention relates to a method of fabrication of a copper platform forsurface enhanced Raman scattering measurements, characterised in that it comprises steps wherein: 0 copper hydride (CuH) is reduced as a result of a pressing process under increased pressure, o the prepared platform is cleaned, preferably using concentrated acetic acid (CH3CO0H). The invention comprises also a copper platform for surface enhancedRaman scattering measurements, obtained with the above method, preferably formeasurements on living cells, where the copper crystallite size is in the range of 30- 120 nm, and where the copper crystallites are uniformly distributed in the volume of the platform and on its surface. Fig. 1 (12 claims) 12
    公开号:SE539710C2
    申请号:SE1450922
    申请日:2014-08-04
    公开日:2017-11-07
    发明作者:Aniela Kowalska Aneta；Michota Kaminska Agnieszka；Adamkiewicz Witold；Tkacz Marek
    申请人:Inst Chemii Fizycznej Polskiej Akademii Nauk；
    IPC主号:
    专利说明:

    Method of fabricating copper platform for surface enhanced Raman scatteringmeasurements and copper platform for surface enhanced Raman scattering meaSUfementS The present invention relates to a method of fabricating copper platform for surface enhanced Fiaman scattering measurements, and a platform fabricated thereby.
    Surface enhanced Fiaman spectroscopy enables spectroscopic studies of very thinfilms and traces of organic compounds. The Fiaman signal is enhanced primarily dueto two parallel processes; i.e., amplification of the electromagnetic field (local fieldenhancement on the metal surface connected with a resonance enhancement of thesurface plasmons - [l/loskovits l/l., J. Fiaman Spectros., 2005, 36, 48S]), andchemical adsorption of analyte molecules on the metal surfaces that enhance theFiaman signal [E. J. Liang and W. Kiefer, J. Fiaman Spectros., 1996, 27, 879; K.Kneipp, H. Kneipp, l. ltzkan, Fi. Fi. Dasari, l/l. S. Feld, Phys. Fiev. Lett., 1997, 78,1667; S. Nie, S. Fi. Emory, Science, 1997,275, 1102].
    The SEFiS signal enhancement depends on a number of factors, including the frequency of excitation radiation, the effective Fiaman scattering cross section} andthe type of analyte. ln addition, it requires the presence of an uneven surface of themetal, the latter being silver, gold or copper. The size of these unevenness features should not exceed the nanometer range.
    The method of fabricating SEFiS platforms has an effect on the nanomorphology ofthe substrate surface, and therefore on the gain obtained in a SEFiS measurement.The ideal method of fabricating SEFiS platforms would lead to fabrication of nanostructures of preset shape, alignment and size within a small tolerance range.
    The most SEFiS substrates reported in the literature are those made of gold or silver.
    The advantage of the silver substrates, compared with the gold ones, is that thebands obtained in the spectrum display higher intensity compared with the goldsubstrates, silver, however, because of its enhanced bactericidal and fungicidal properties, causes necrosis of the living cells studied, due to, e.g., DNA denaturation [K. Kneipp, Y. Wang, H. Kneipp, l. Itzkan, R. R. Dasari, and l/l. S. Feld, Phys. Rev.Lett., 1996, 76, 2444; K. Kneipp, H. Kneipp, V. B. Kartha, R. l/lanoharan, G. Deinum,l. Itzkan, R. R. Dasari, l/l. S. Feld, "Detection and identification of a single DNA basemolecule using surface-enhanced Raman scattering (SERS)." Phys. Rev. E 57,R6281-R6284 (1998)]. The literature includes reports presenting differences inspectral fingerprinting for viable and non viable cells [A. E. Grow, L L Wood, J.
    L. Claycomb, P. A. Thompson, J. l/licrobiol. l/lethods, 2003, 53, 221 -233]. Therefore,copper platforms, as less bactericidal and more stable in time, are more promising for SERS measurements, in particular for living cell studies.
    There are a few procedures that can be used to fabricate SERS platforms, includingelectrochemical metal deposition on electrodes [J. Cejkova, V. Prokopec, S.Brazdova, A. Kokaislova, P. l/latejka, F. Stepanek, Applied Surface Science, 2009,255, 7864-7870; A. Kokaislova, S. Brazova, V. Prokopec, l/l. Clupek, J. Cejkova, P.l/latejka, Chem. Listy 2009, 103, 246], electrochemical surface modification [Q. Shao2012, J. Bukowska, K. Jackowska, Electrochim. Acta, 1990, 35, 315 lithography [l/l.Kahl, E. Voges, S. Kostreewa, C. Viets, W. Hill, Sens. Actuators B 1998, 51, 285],metal vapour deposition [N. Horimoto, N. lshikawa, A. Nakajima, Chem. Phys. Lett.2005, 413, 78]. All the methods disclosed require specialized research equipmentand are quite time-consuming when performed. lt has to be noted thatelectrochemical methods used mostly for producing copper wafers do not guaranteethat uniformly distributed crystallites of equal size are obtained on the fabricated surfaces.
    The present invention provides a method of fabricating platforms, also referred to asthe substrates, that are uniform on the entire surface, relatively easy in preparation,do not require high costs and guarantee that good Raman signal enhancementfactors are obtained. ln addition, the fabricated substrates do not cause necrosis ofliving cells to the extent as in the case of silver, and can be used in medicaldiagnostics. Therefore, the substrates produced with the method according to thepresent invention can be used as so-called platforms for surface enhanced Raman scattering measurements of cells.
    The platform "uniformity" mentioned in the previous paragraph and used throughout this description of the invention, shall be understood as follows: a platform accordingto the present invention is characterised in that it comprises copper crystallites of aspecific size (30 - 120 nm), uniformly (homogenously) distributed in space (i.e., in thevolume of the platform) and on the platform's surface, in particular on the surfacewhere cells or analyte molecules are placed to perform SERS measurements. ln spite of the vast number of literature reports and patent applications, there ispresently no method available that would guarantee the fabrication of coppersurfaces allowing for a suitable signal enhancement, comparable with those obtainedfor silver platforms and guaranteeing reproducibility of the recorded SERS spectra.Below, relevant patent applications disclosing the fabrication of copper surfaces forSERS measurements are presented: The US patent US6406777 (B1), "l/letal and glass structure for use in surfaceenhanced Raman spectroscopy and method for fabricating same" provides structuresfor detection of organic contaminants in air and aqueous environments, and metallicand anionic contaminants in water. The structures are fabricated by etching a surfaceof a glass substrate to form a roughened surface with an adhesion layer on thatsurface; then metals such as gold, silver, or copper are deposited on the adhesionlayer to create a composite structure, and subsequently the composite structure isplaced in a thiol solution selected so that the structure selectively attracts an analyteof interest. The authors postulate that the roughened surface for a SERS enhancedresponse has an average surface roughness that does not exceed 2500 A and aperiodicity that does not exceed 12.5 microns, they do not mention, however, themagnitude of the SERS enhancement factor.
    The publication WO2006060734 (A2), "Nanostructured substrate for enhancedRaman scattering" discloses the method of fabricating a uniformly nanostructuralSERS substrate. For instance, the surface of the substrate may comprise metalnanoparticles such as silver, copper, gold. The nanoparticles can be spheroidal,which guarantees that the diameter of the produced metal particles is contained in arange of 40 - 120 nm. The reproducibility of the fabricated films and the SERS enhancement factors were not reported.
    The publication CN 1027 59520 (A), "Preparation method of active radical withsurface-enhanced Raman scattering (SERS) effect" discloses the method ofpreparation of an active radical surface for use in SERS measurements. ln themethod, firstly, large nanoporous silicon columnar structures are prepared, and thennanowires of a Jl-Vl group compound semiconductor (such as zinc oxide, titaniumdioxide, cadmium sulfide, cadmium selenide, etc.) are formed on the columnarstructures, to finally deposit metals such as gold, Silver, copper, on the nanowirestructures. The authors claim that the method disclosed is fast, highly selective andcan be used for determination of traces of chemical substances, they do not presentany data concerning the SERS measurements for these surfaces.
    The publication US 2008/0096005 A1, “Nanostructured substrate for surfaceenhanced Raman scattering", relates to fabrication of surfaces made of silicondioxide, aluminium dioxide, or titanium dioxide coated with Ag, Au, or Cunanoparticles of 20 - 140 nm size. For Escherichia coli adsorbed on one of the typicalsurfaces the enhancement factor of 2 x 104 was obtained. No information as to thereproducibility of the fabricated surfaces was reported.
    The US patent US 7879625 B1, "Preparation of SERS substrates on silica-coatedmagnetic microspheres" discloses SERS substrates composed of magneticmicroparticles complexed with metal colloidal particles. The authors of the patentmention that the substrates can be used for the detection of fungi, viruses, andbacteria, etc., the substrates are, however, of single use. Therefore, the purpose ofthe present invention is to develop a method for preparation of a substrate, as littlebactericidal as possible for cells, allowing for the detection and identification of livingorganisms, using the surface enhanced Raman scattering (SERS) technique that isfree of the drawbacks mentioned above.
    The method of fabrication of a copper platform for surface enhanced Ramanscattering measurements, according to the present invention, is characterised in thatit comprises steps wherein: - copper hydride (CuH) is reduced as a result of a pressing process under increased pressure, - the prepared platform is cleaned, preferably using concentrated acetic acid(CH3COOH).
    Preferably, the pressing step is carried out using a hydraulic press.
    Preferably, the pressing process is composed of two steps, allowing a relaxation timeof material in the platform.
    Preferably, the product is pressed under pressure from 476 l/lPa to 1013 l/lPa,preferably from 571 lVlPa to 973 lVlPa, and most preferably from 663 l/lPa to 713l/lPa. ln preparation of the platform according to the present invention, application of agiven pressure results in platforms for SERS measurements with a preset size ofcopper crystallites, and therefore applying a pressure of: - 476 l/lPa enables to obtain copper crystallites of 30 - 120 nm size, - 571 l/lPa enables to obtain copper crystallites of about 30-90 nm size, -the most preferred range of 663 - 713 l/lPa allows for obtaining a narrow range of copper particle sizes, of 30 - 60nm, and in turn - 843 l/lPa and 973 l/lPa result in copper crystallites of 30 - 90 nm, - whereas application of 1013 l/lPa allows for obtaining copper crystallites in a broader size range of 30 - 120 nm. l/lost preferably, the pressure 663 l/lPa is used, and the relaxation time of material in the platform is 30 minutes.
    Preferably, the platform is cleaned by immersing. ln such a case, preferably, the immersion time is up to 30 seconds.Preferably, after the cleaning step, the acid reminders are removed by blowing the platform through with an inert gas. ln such a case, preferably, gaseous argon or nitrogen is used.
    Preferably, pure and dried CuH is used in the pressing process, and before theprocess the CuH is stored at a temperature lower than -78°C, in particular in dry ice.ln such a case, preferably, the pressing process is performed immediately aftertaking out CuH from a low temperature storage, in particular from dry ice.
    The invention comprises also a copper platform for surface enhanced Ramanscattering measurements, obtained with the above method, preferably formeasurements on living cells, where the copper crystallite size is in the range of 30 -120 nm, and where the copper crystallites are uniformly distributed in the volume of the platform and on its surface.
    Preferred embodiments of the invention The present invention is now explained more in detail in a preferred embodiment, with reference to the accompanying figures, wherein: Fig. 1 shows three SEl/l images of the fabricated copper substrates, recorded uponapplication of the following pressures: (a) 476 l/lPa, (b) 663 lVlPa, and (c) 1013 lVlPa.
    Fig. 2 shows SERS spectra of malachite green isothiocyanate, used at 10-GlVlconcentration as a standard adsorbed on selected copper substrates at selected pressures, resulting in different enhancement factors.
    The method disclosed in the present patent application leads to fabrication of a copper platform that can serve as a substrate for SERS studies on living cells. lnitially, pure and dried CuH is obtained with a method available in the literature. The obtained product is then placed in small containers, in an amount needed to preparea single platform in each container. Subsequently, the containers are placed in the dry ice and, additionally, at low temperature.
    The pellet press is then prepared for use by polishing and washing it with ethanol toremove possible contaminants. After this step, the surface of the pellet presscontacting the prepared product is coated with a small amount of paraffin oil, thus allowing for uniform pressure on the entire pressed surface.
    Subsequently, immediately after taking out from the dry ice, the prepared product(CuH) is placed in the pellet press and promptly subject to the procedure offabrication of the copper films by reduction of copper hydride under high pressure, using a hydraulic press for that purpose. lmmediate cooling down of the obtained product, as well as immediate processingthereof just after taking out from the dry ice, is important because of the stability ofthe material used. Copper hydride is preferably stored at -78°C, a temperature atwhich it is the most stable [Whitesides G. l/l., Filippo J. 5., 5treronsky Jr. E. R., CaseyC. P., J. Am. Chem. Soc. 1969, 5, 6542-6544].
    The following procedure was employed: 1) 663 l/lPa, and leaving the material for 30 minutes; 2) then a pressure 663 l/lPa was applied, and the material was allowed to relax for 30 minutes. ln other embodiments the pressures 476 lVlPa, 571 lVlPa, and 1013 lVlPa, wereappfied.
    Just before use, a copper platform so fabricated, is cleaned to remove copper oxides produced almost immediately on the copper surface, using concentrated acetic acid (CHSCOOHL by immersing the platform in the acid for up to 30 s. Then, acidreminders are removed by delicately blowing the surface through with an inert gas and the platform is immersed in the analyte solution.
    Fig. 1 shows three SEl/l images of copper substrates fabricated using the followingpressures: (a) 476 lVlPa, (b) 663 lVlPa, and (c) 1013 lVlPa.
    SERS measurements were performed on platforms obtained with the aforementionedmethod at different pressures, using malachite green isothiocyanate as standard at a1O'6l/l (CsEns) molar concentration, and as reference the spectrum of the standardrecorded in the normal Raman spectroscopy mode at a 0.5 l/I (Co) concentration.Using the formula EF= (Isene x Co )/(10 x Csens) for a 1171 cm* band, theenhancement factor, EF = 2,77 X 107, was obtained. Typical measurement results are shown in Fig. 2.
    The setup for the pressure-based fabrication of the copper platform includes: - hydraulic press, - pressure gauge to measure the pressure force, - pellet press.
    Acknowledgement The fees related to protection of the invention have been financed from the funds ofthe project NanOtechnology, Biomaterials and aLternative Energy Source for ERAintegration FP7-REGPOT-CT-2011-285949-NOBLESSE.
    权利要求:
    Claims (11)
    [1] 1. Method of fabrication of a copper platform for surface enhanced Raman scattering measurements, characterised in that it comprises steps wherein: - copper hydride (CuH) is subjected to a pressing process under increased pressure, - the prepared platform is cleaned, preferably using concentrated acetic acid(CH3COOH).
    [2] 2. Method according to c|aim 1, characterised in that the pressing step is carried out using a hydraulic press.
    [3] 3. l/lethod according to c|aim 1 or 2, characterised in that the product is pressedunder pressure from 476 l/lPa to 1013 l/lPa, preferably from 571 l/lPa to 973 l/lPa,and most preferably from 663 IVIPa to 713 l/lPa.
    [4] 4. l/lethod according to c|aim 3, characterised in that the pressure 663 l/lPa is used, and the relaxation time of material in the platform is 30 minutes.
    [5] 5. l/lethod according to any of claims from 1 to 4, characterised in that the platform is cleaned by immersing.
    [6] 6. l/lethod according to c|aim 5, characterised in that the immersion time is up to 30 seconds.
    [7] 7. l/lethod according to any of claims from 1 to 6, characterised in that the acid reminders are removed by blowing the platform through with an inert gas.
    [8] 8. l/lethod according to c|aim 7, characterised in that gaseous argon or nitrogen is used.
    [9] 9. Method according to any of claims from 1 to 8, characterised in that pure anddried CuH is used in the pressing process, and before the process the CuH is storedat a temperature lower than -78 °C, in particular in dry ice.
    [10] 10. l/lethod according to claim 9, characterised in that the pressing process isperformed immediately after taking out CuH from a low temperature storage, inparticular from dry ice.
    [11] 11. Copper platform for surface enhanced Raman scattering measurements,obtained with the method according to any of the above claims, preferably formeasurements on living cells, where the copper crystallite size is in the range of 30 -120 nm, and where the copper crystallites are uniformly distributed in the volume ofthe platform and on its surface.
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    同族专利:
    公开号 | 公开日
    PL224282B1|2016-12-30|
    SE1450922A1|2015-02-07|
    PL404988A1|2015-02-16|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    法律状态:
    2019-04-02| NUG| Patent has lapsed|
    优先权:
    申请号 | 申请日 | 专利标题
    PL404988A|PL224282B1|2013-08-06|2013-08-06|Method of obtaining a copper platform for the measurements of surface-strengthened Raman effect and the copper platform for the measurements of surface-strengthened Raman effect|
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