Patents

1. Platform for Surface Enhanced Raman Spectroscopy”, Patent, 219706 (2014) Poland; IN-564/MUM/2011 India; Patent UA 109104 (2014), Ukraine; RU 20111110372 Russia; Patent US 8,531,660 (2014) USA; I. Dzięcielewski, R. Hołyst, A. Michota-Kamińska, S. Porowski, T. Suski, J. Weyher.

The present invention is a platform for measurement of surface-enhanced Raman effect (SERS), covering the surface of nitride containing gallium, coated with metal selected from among gold, silver, platinum, copper and/or alloys thereof. Development of a platform based on the surface of nitride developed using photo-etching technique, with the use of platinum as a catalyst in such a way that they form whiskers of the nitride containing gallium, inside of which there linear defects are present, optionally collected in tufts, further coated with a layer of the corresponding metal (deposition of “electroless” from solutions and evaporation in vacuum). The resulting platform is characterized by high repeatability of morphology of the nanostructures building it, which ensures high reproducibility of the obtained SERS signals - one of the most important parameters of the substrates for Raman analyses.

2. Method for deposition of metal nanoparticles onto surface, the surface obtained by this process and its use, countries: Patent CH 703728, 2014, Switzerland; PL 220942, 2014, Poland; J. Niedziółka-Jonsson, I. Kaminska, A. Michota-Kamińska, M. Opałło, R. Hołyst.

 The present invention relates to a process for the deposition of metal nanoparticles on the electrode surface, the so covered surface and its uses a platform for the measurements using methods employing surface plasmon resonance, i.e. surface-enhanced Raman effect (SERS), and localized surface plasmon resonance (LSPR).

3. Method of hydrophilic coating of solid gold layer with a developed surface, Patent-219899, Poland, 2014, Patent CH 703612, 2014, Switzerland; K. Winkler, M. Fiałkowski, A. Michota-Kamińska, R. Hołyst.

 The present invention is a method of coating the surface of the hydrophilic solids (metals, semiconductors and dielectrics), in particular silicon, glass, indium tin oxide (ITO), aluminum gallium nitride, gold structures, with a strong surface, here in after referred to as the golden “nano-flowers” or “micro-flowers”. To the method according to the invention, aqueous solutions of tetrachloroauric acid and hydroxylamine hydrochloride are used.

4. Application of borohydride for purification of the Surface Enhanced Raman Spectroscopy platforms containing a layer of gold, Patent; CH 703842, 2014; V. Sashuk, A. Michota-Kamińska, R. Hołyst, M. Fiałkowski.

 The present invention is a chemical method of regeneration of platforms for measuring the surface-enhanced Raman effect (Patent, 219706 (2014), A. Kamińska, R. Hołyst, J. Weyher, I. Dzięcielewski, T. Suski, S. Porowski: “Platform for Surface Enhanced Raman Spectroscopy”. The so far, commercially available substrate for SERS measurements are disposable materials. The regeneration platform for SERS measuring is of utmost importance for economic reasons. An effective chemical method for the platform regeneration based on aqueous or aqueous-alcoholic solutions containing an oxidant or reducer with/without pH regulators was developed. In one embodiment the said solution is an aqueous solution of ammonia and hydrogen peroxide or an aqueous solution of ammonium persulfate. Regeneration of the platform for SERS measuring mainly involves cleaning, or removal of objects of various chemical or biological origin from the surface of the substrate (molecules adsorbed chemically or physically on the surface).

5. The solid surface covering method by two-dimensional network of nanoparticles and a solid surface covered by this metod, Patent, PL 218683, Poland (2015); J. Paczesny, K. Sozański, A. Żywociński, W. Adamkiewicz, I. Dzięcielewski, K. Winkler, A. Michota-Kamińska, R. Hołyst.

 The present invention is a method of coating the surface of a solid with two-dimensional network of nanoparticles using Langmuir-Blodgett technique. The suitably prepared mixture of nanoparticles and the liquid crystal compound 8CB (4'-n-octyl-4-cyanobiphenyl) when applied to the surface creates a two-dimensional network of nanoparticles, wherein the network cell size can be easily controlled. The invention also relates to a method to select of optimal process parameters to achieve a network of a particular morphology. The invention also includes solid surface coated by this method.

6. SERS measurement platform and a method for its manufacture, Patent CH 703728 (2015), Patent PL 218683, Poland, J. Paczesny, K. Sozański, A. Żywociński, W. Adamkiewicz, I. Dzięcielewski, K. Winkler, A. Michota-Kamińska, R. Hołyst.

 The present invention is a stable and effective platform for the surface-enhanced Raman scattering measurments. It is made of micro-flowers of gold (Au MFs) deposited on the substrate covered with nanowires of gallium nitride (GaN). For the preparation of such a platform a three-step process is used. In the first stage a two-dimensional network of gold nanoparticles (Au NPs) is applied on the solid substrate, using Langmuir-Blodgett technique (LB). The second stage is the growth of nanowires of gallium nitride (GaN) using the chemical vapor deposition method(CVD). Since in CVD process gold plays the role of a catalyst, GaN nanowires are formed only in areas where, in the first stage, Au NPs were deposited. The third stage is the deposition of micro-flowers of gold that are deposited preferentially on GaN nanowires, rather than in the spaces between them. Thus prepared surface is mechanically stable and proves excellent properties as a substrate for SERS over time. The invention also relates to a method for the selection of the most desired parameters to carry out each of the stages.

7. Method for depositing metal nanoparticles on the surface and platform to the measurements SERS or LSPR, Patent, PL 220820, Poland, Patent NL 2009442, 2014, Netherlands, M. Siek, J. Niedziółka-Jönsson, M. Opałło, A. Michota-Kamińska, A. Kelm, R. Hołyst

 The present invention is a stable and effective platform for the surface-enhanced Raman scattering measurments.

8. The platform and its use for the detection and / or identification of microorganisms, especially bacteria, via the technique of surface enhanced Raman effect and a method for the deposition of these microorganisms on produced platforms. 2018, 232520 (P-406900), Poland; T. Szymborski, E. Witkowska, W. Adamkiewicz, J. Waluk, A. Michota-Kamińska

The present invention is a process for the preparation of SERS-active nanostructures based on electrospun polymer mat (PLLA, Nylon and other) and nanometric gold layer sputtered via magnetron sputtering. The enhancement factor for this platform is 105-106, stability in time up to 2 months and correlation coefficient of recorded SERS signals is 0.65-0.87. This platform is dedicated for filtration, immobilization and detection of bacteria from fluids (blood, urine, water etc.).

9. Method of fabricating copper platform for surface enhanced Raman scattering measurements and copper platform for surface enhanced Raman scattering measurement, 2013, P-404988 Poland; A. Kowalska, A. Michota-Kamińska, W. Adamkiewicz, M. Tkacz.

 The present invention is a method of obtaining a copper platform for measurements of surface-enhanced Raman effect, characterized in that it comprises the steps in which the copper hydride is reduced as a result of the pressing process under increased pressure. The resulting platform is further subjected to cleaning with concentrated acetic acid. The invention also includes a platform of copper to measure surface-enhanced Raman effect, obtained by the above method, wherein the crystallite size of copper is 30 - 120 nm are distributed uniformly on the surface of the platform. This platform is particularly designed for measuring living cells like bacteria.

Patent applications

1. The method of uniform coating of the silver surface by electrochemically roughened gold layer with a highly developed surface and the platform for measuring the surface-enhanced Raman effect, in particular for bacteria, 2013, P-402089; E. Witkowska, S. Arumugam, A. Michota-Kamińska, W. Adamkiewicz, J. Waluk.

 The present invention relates to a process for uniform coating of electrochemically roughened surface of silver with the layer of gold with a highly developed surface, characterized in that it comprises the following steps: a) electrochemical roughening of Ag electrode by cyclic voltammetry, (b) creating an electrochemical cell in a solution containing soluble salts of gold, wherein the working electrode is just roughened Ag electrode, (c) electrodeposition of gold nanostructures on a silver substrate resulting in gold and silver hybrids.

2. A method for preparing a platform for testing of chemicals via surface-enhanced Raman spectroscopy (SERS) and platform obtained by this method, 2013, P-406026; E. Guziewicz, D. Snigurenko, T. Szymborski, E. Witkowska, A. Michota-Kamińska

The present invention is a process for the preparation of a platform for measurements of chemicals using surface-enhanced Raman spectroscopy and a platform obtained in this way. More particularly, the present invention reveals a new surface for SERS analysis based on the zinc oxide layer obtained by atomic layer deposition method (ALD) coated with highly developed gold surface.

3. The platform for testing of chemicals and microorganisms via Surface Enhanced Raman Spectroscopy and method of its preparation. 2014, P-409210; E. Witkowska, T. Szymborski, J. Waluk, A. Michota-Kamińska

The subject of the invention is a platform for the study of chemical substances and microorganisms using the technique of surface enhanced Raman spectroscopy and the platform was obtained. The invention reveals a new surface for analysis of Surface-enhanced Raman Spectroscopy (SERS) based on a layer of polymer nanofibres made with the Forcespinning technique, with a highly developed gold-coated surface.

4. The method of detection of bacteria: Salmonella spp, Cronobacter spp oraz Listeria monocytogenes from food samples, 2016, P-416927, Poland; E. Witkowska, D. Korsak, M. Księżopolska- Gocalska, A. Michota-Kamińska

The present invention is a method of the detection of the Salmonella spp, Cronobacter spp., and Listeria monocytogenes bacteria in food matrices (salmon, eggs, powdered infant formula milk, mixed herbs) including the procedure of distinguish L. monocytogenes from L. ivanovii by coupling the surface-enhanced Raman spectroscopy with with principal component analysis (PCA).

5.  Platform for surface-enhanced Raman effect, method of preparing such a platform, method for determining substances and / or microorganisms using such a platform, use of such a platform for direct detection and / or identification of substances and / or microorganisms, especially bacteria, using the surface-enhanced Raman effect technique or in combination with electrochemical measurements. 2018, P. 426643, Poland; K. Niciński, E. Witkowska, D. Korsak,  J. Trzcińska-Danilewicz, A. Girstun, T. Szymborski, A. Michota-Kamińska

We have developed a SERS platform with a high enhancement factor, high repeatability and stability that would allow for the electrical potential to be applied (i.e. useful for spectroelectrochemical measurements) and capable of providing suitable surface for measuring spectra of microorganisms, especially bacteria, using the surface-enhanced Raman scattering technique (SERS). The platform can be used for SERS measurements of  various biological and organic samples. Main element of a platform is photovoltaic cell  of which bottom layer consist of metal, constituting the bottom electrode. Upper part is covered with a layer of doped silicon equipped with a anti-reflective layer, on the surface of which the electrode leads are located. Additionally SERS-active metallic layer is deposited on the anti-reflective surface.

6. Platform for the detection and/or identification of microorganisms, especially bacteria, using the Surface Enhanced Raman Effect (SERS) technique, the method of preparation, application and measuring using such a platform. 2018, P.424152, Poland; T. Szymborski, E. Witkowska, K. Niciński, A. Michota-Kamińska

The object of the invention is a platform for the detection and/or identification of microorganisms, especially bacteria, using the Surface Enhanced Raman Effect (SERS) technique, comprising a substrate that is a dense weave fabric with filtration properties (filter fabric) covered with a metallic layer, characterised by the fact that the filter fabric is non-meshless, in which the braid consists of warp wires interlaced with weft wires to form a dense weave and in which the warp wires have a diameter different from that of the weft wires, and in addition is made of a material with a thermal conductivity of not less than 10 W/m*K. The non-meshless fabric, i.e. the meshes should not be visible in the XY plane of the fabric so that the biological material, e.g. bacteria, is retained on the surface of the wires.

7. Method for detecting thermotolerant bacteria of the genus Campylobacter spp. in food. 2019, P.430701, Poland; E. Witkowska, K. Niciński, B. Dominiak, D. Korsak, J. Waluk, A. Michota-Kamińska

We have developed a new approach applying novel silver/photovoltaic-based (Ag/PV) SERS substrates in the detection of foodborne bacteria, namely thermotolerant Campylobacter spp., in different poultry samples. The presented method of bacteria identification based on the SERS technique challenges the standard biochemical methods in terms of simplicity, specificity and rapidity, and thus may significantly influence the future of microbiology and medical diagnosis.

8. Flexible platform for surface-enhanced Raman effect, method of preparing such a platform, method of determining substances and / or microorganisms using such a platform, using such a platform for direct detection and / or identification of substances and / or microorganisms, especially bacteria and cancer cells using the technique surface enhanced Raman effect. 2019  P.430767, Poland; M. Czaplicka, A. Nowicka,  T. Szymborski, A. Kowalska, J. Trzcińska-Danilewicz, A. Girstun, A. Michota-Kamińska

The goal of the invention was to develop a platform with a high enhancing factor, high repeatability, stability, ease of processing, e.g. by cutting and bending, which would allow the application of electrical potentials (deposition of bacteria / cancer cells using the DEP effect), and thus capable of measuring microorganisms, and especially bacteria, using the SERS technique.

9. The method of deposition of microorganisms or cancer cells on the SERS platform using a dielectrophoretic effect and identification of microorganisms or cancer cells on the SERS platform. 2020, P.433801, Poland; T. Szymborski, A. Nowicka, M. Czaplicka, J. Trzcińska-Danilewicz, A. Girstun, and A. Michota-Kamińska

The subject of the invention is the method of deposition of microorganisms (mainly bacteria) or cancer cells with the use of the negative dielectrophoretic effect (n-DEP). In the proposed patent application we apply an alternating electric field between two electrodes. Main electrode is a flexible SERS platform on which the examined objects are deposited due to dielectrophoretic force. After depositing with the use of n-DEP technique we identify bacteria/cancer cells via surface enhanced Raman spectroscopy (SERS) technique. The invention is used in microbiological laboratories.

10. The method of manufacturing a silicon platform for SERS measurements, silicon platform for SERS measurements and the use of a silicon platform for SERS measurements of biological samples. 2020, P.434300, Poland; T. Szymborski, Y. Stepanenko, P. Piecyk, K. Niciński, and A. Michota-Kamińska

The first object of the invention is the method of manufacturing a silicon platform with femtosecond laser. The second object  of the invention is a silicon platform for SERS measurements. Another object of invention is the application of the platform for direct detection and/or identification of biological or chemical samples using a surface enhanced Raman spectroscopy (SERS).

11. The method for determining the presence of venereal disease pathogens. 2020, P.436251, Poland; S. Berus, B. Młynarczyk-Bonikowska, M. Adamczyk-Popławska, T. Szymborski, E. Witkowska-Iwan, and A. Michota-Kamińska

We have developed a novel approach for detection pathogens responsible for sexually transmitted disease (STD). The present method is based on a SERS technique combined with chemometric analysis (PCA, PLS-DA). Since a new method enable fast (ca. 15 minutes), simple, label-free and accurate identification of pathogens, this new invention may significantly influence the future of diagnosis STD in real clinical samples.