JP2016197114A - 量子結晶基板 - Google Patents
量子結晶基板 Download PDFInfo
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- JP2016197114A JP2016197114A JP2016128252A JP2016128252A JP2016197114A JP 2016197114 A JP2016197114 A JP 2016197114A JP 2016128252 A JP2016128252 A JP 2016128252A JP 2016128252 A JP2016128252 A JP 2016128252A JP 2016197114 A JP2016197114 A JP 2016197114A
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- 239000013078 crystal Substances 0.000 title claims abstract description 43
- 239000000758 substrate Substances 0.000 title claims description 43
- 229910052751 metal Inorganic materials 0.000 claims abstract description 98
- 239000002184 metal Substances 0.000 claims abstract description 98
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 47
- 229910052709 silver Inorganic materials 0.000 claims abstract description 39
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004332 silver Substances 0.000 claims abstract description 38
- 239000007864 aqueous solution Substances 0.000 claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000003446 ligand Substances 0.000 claims abstract description 14
- 238000004519 manufacturing process Methods 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052802 copper Inorganic materials 0.000 claims abstract description 9
- 239000010949 copper Substances 0.000 claims abstract description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052737 gold Inorganic materials 0.000 claims abstract description 8
- 239000010931 gold Substances 0.000 claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001092 metal group alloy Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 3
- 239000011701 zinc Substances 0.000 claims abstract description 3
- 238000005259 measurement Methods 0.000 claims description 9
- -1 amino acid ions Chemical class 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
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- 108091007433 antigens Proteins 0.000 claims description 5
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- 239000002270 dispersing agent Substances 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 239000002096 quantum dot Substances 0.000 abstract description 18
- 230000000694 effects Effects 0.000 abstract description 17
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- 238000001179 sorption measurement Methods 0.000 abstract 1
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- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 14
- 229910000906 Bronze Inorganic materials 0.000 description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 13
- 239000010974 bronze Substances 0.000 description 13
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 13
- 230000005284 excitation Effects 0.000 description 10
- 239000000523 sample Substances 0.000 description 9
- 238000007740 vapor deposition Methods 0.000 description 9
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- 239000000126 substance Substances 0.000 description 8
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- 238000001237 Raman spectrum Methods 0.000 description 6
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- 229940024606 amino acid Drugs 0.000 description 5
- VYXSBFYARXAAKO-WTKGSRSZSA-N chembl402140 Chemical compound Cl.C1=2C=C(C)C(NCC)=CC=2OC2=C\C(=N/CC)C(C)=CC2=C1C1=CC=CC=C1C(=O)OCC VYXSBFYARXAAKO-WTKGSRSZSA-N 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- YBJHBAHKTGYVGT-ZKWXMUAHSA-N (+)-Biotin Chemical compound N1C(=O)N[C@@H]2[C@H](CCCCC(=O)O)SC[C@@H]21 YBJHBAHKTGYVGT-ZKWXMUAHSA-N 0.000 description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 4
- PXIPVTKHYLBLMZ-UHFFFAOYSA-N Sodium azide Chemical compound [Na+].[N-]=[N+]=[N-] PXIPVTKHYLBLMZ-UHFFFAOYSA-N 0.000 description 4
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- 229910001961 silver nitrate Inorganic materials 0.000 description 4
- ZSILVJLXKHGNPL-UHFFFAOYSA-L S(=S)(=O)([O-])[O-].[Ag+2] Chemical compound S(=S)(=O)([O-])[O-].[Ag+2] ZSILVJLXKHGNPL-UHFFFAOYSA-L 0.000 description 3
- 150000001413 amino acids Chemical class 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
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- DHCDFWKWKRSZHF-UHFFFAOYSA-N sulfurothioic S-acid Chemical compound OS(O)(=O)=S DHCDFWKWKRSZHF-UHFFFAOYSA-N 0.000 description 3
- 238000000015 thermotherapy Methods 0.000 description 3
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- 229910021607 Silver chloride Inorganic materials 0.000 description 2
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- 238000001514 detection method Methods 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 description 2
- 108090001008 Avidin Proteins 0.000 description 1
- QNAYBMKLOCPYGJ-UHFFFAOYSA-N D-alpha-Ala Natural products CC([NH3+])C([O-])=O QNAYBMKLOCPYGJ-UHFFFAOYSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-UWTATZPHSA-N L-Alanine Natural products C[C@@H](N)C(O)=O QNAYBMKLOCPYGJ-UWTATZPHSA-N 0.000 description 1
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 1
- KDXKERNSBIXSRK-UHFFFAOYSA-N Lysine Natural products NCCCCC(N)C(O)=O KDXKERNSBIXSRK-UHFFFAOYSA-N 0.000 description 1
- 239000004472 Lysine Substances 0.000 description 1
- 206010037660 Pyrexia Diseases 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- 229960003767 alanine Drugs 0.000 description 1
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005672 electromagnetic field Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- ZBKIUFWVEIBQRT-UHFFFAOYSA-N gold(1+) Chemical compound [Au+] ZBKIUFWVEIBQRT-UHFFFAOYSA-N 0.000 description 1
- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 125000003588 lysine group Chemical group [H]N([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])(N([H])[H])C(*)=O 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
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- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000002331 protein detection Methods 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 238000004080 punching Methods 0.000 description 1
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 150000003378 silver Chemical group 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/64—Thiosulfates; Dithionites; Polythionates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82B—NANOSTRUCTURES FORMED BY MANIPULATION OF INDIVIDUAL ATOMS, MOLECULES, OR LIMITED COLLECTIONS OF ATOMS OR MOLECULES AS DISCRETE UNITS; MANUFACTURE OR TREATMENT THEREOF
- B82B3/00—Manufacture or treatment of nanostructures by manipulation of individual atoms or molecules, or limited collections of atoms or molecules as discrete units
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G5/00—Compounds of silver
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C229/02—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton
- C07C229/04—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated
- C07C229/06—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton
- C07C229/08—Compounds containing amino and carboxyl groups bound to the same carbon skeleton having amino and carboxyl groups bound to acyclic carbon atoms of the same carbon skeleton the carbon skeleton being acyclic and saturated having only one amino and one carboxyl group bound to the carbon skeleton the nitrogen atom of the amino group being further bound to hydrogen atoms
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
- C07F1/10—Silver compounds
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/63—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light optically excited
- G01N21/65—Raman scattering
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Abstract
Description
そこで、原点に帰って考えると、プラズモン現象における増強の大きさは金属表面における電磁場に関する吸着分子中に存在するさまざまな結合の位置及び配向を含む多数のパラメータに依存するといわれるので、SERS法における最適基板を提供し、再現性を確保するためにはSERS現象が生ずるメカニズムに関与する(i)入射光の局所的強度を増強する金属中の表面プラズモン共鳴の最適物理的状況の達成と(ii)金属表面とラマン活性分子との間の電荷移動錯体の形成及びその後の遷移という最適化学的状況の達成が必要であり、最適物理的状況の達成のためには、最適状態への粒子サイズ及び配列の制御が難しいものの、蒸着法の採用も可能であるが、蒸着法では同時に電荷移動錯体の形成という最適化学的状況を達成することができないという観点に達した。
2)また、金属錯体は金属成分がイオン化しやすい状態にあり、(ii)イオン化金属表面にラマン活性分子が吸着して電荷移動錯体を形成するため、最適化学状態を達成し、再現性のよい結果を招来する。
3)金属錯体は電荷の調整によりタンパク質であるウイルス等を吸着しやすい電荷をもつことができ、例えば量子ドットにタンパク質アビジン又は生体物質ビオチンを結合させた量子ドットを合成し、タンパク検出に好適なSERS基板も形成させることができる。
4)金属錯体水溶液に抗体を分散させ、金属錯体ともに担体上に析出させると、抗体の選択により適切な抗原のみを吸着して抗原抗体反応を検出することができる。
5)金属針を担体として本発明の量子結晶を針先に形成すれば、患部に直接金属針を挿入してレーザ光を照射することによりプラズモン効果を利用して温熱療法を実施することができる。
本発明においては図7(a)〜(c)に示すように、ガラス又はプラスチック板1上に円形打ち抜き成形して皿上の0.1mm程度の薄い金属板2を貼り付けて製造することができる。この基板は金属部分2が皿状に形成されるので、上記分散液を滴下すると、液滴3となって盛り上がる(図7(b))。その後液滴を窒素ブロー等で吹き飛ばすと、金属錯体が析出して凝集域4が金属表面上に形成されて金属ナノクラスタを量子ドットとする測定基板が作成される(図7(c))。薄い金属板2に代え、金属膜を化学鍍金、蒸着により形成するようにしてもよい。
Claims (10)
- 金、銀、銅、ニッケル、亜鉛、アルミニウム又は白金から選ばれるプラズモン金属と配位子とからなるプラズモン金属錯体水溶液を用意し、プラズモン金属より電極電位が卑なる金属又は金属合金またはプラズモン金属より卑なる電極電位を持たせた金属からなる担体と接触させてプラズモン金属錯体を析出させ、プラズモン増強効果を有する量子結晶を前記金属担体上に配列することを特徴とするプラズモン増強効果を有する金属錯体量子結晶の製造方法。
- 前記担体が金属基板、金属粒子、金属針、キャピラリー内金属膜である請求項1記載の製造方法。
- 量子結晶がプラズモン金属のナノクラスターを内包して前記金属担体上に配列され、ナノクラスターが平均数ナノから十数ナノメートルサイズのクラスターである請求項1記載の製造方法。
- 前記金属担体上で形成された金属錯体の量子結晶中のナノクラスターを形成するプラズモン金属の少なくとも一部が配位子とイオン結合状態にある請求項1記載の製造方法。
- プラズモン金属錯体がアミノ酸イオン、アンモニアイオン、チオ硫酸イオン及び硝酸イオンの1種を配位子として形成される請求項1記載の製造方法。
- 前記プラズモン金属が金、銀または銅から選ばれる請求項1記載の製造方法。
- プラズモン金属錯体水溶液が500ppmから5000ppmの濃度である請求項1記載の製造方法。
- プラズモン金属錯体水溶液が500ppmから2000ppmの濃度である請求項1記載の製造方法。
- 銀ナノクラスタに対する分散剤のモル分率が銀原子量換算で1/50〜1/150である請求項1記載の製造方法。
- プラズモン金属錯体水溶液に抗体を添加し、金属基板上に抗体とともに金属錯体を析出させ、対応する抗原に特異的に反応する抗原−抗体反応用測定基板とする請求項1記載の製造方法。
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WO2013065747A1 (ja) * | 2011-10-31 | 2013-05-10 | 有限会社マイテック | 金属錯体量子結晶及びそれを用いる生化学物質の表面増強ラマン散乱(sers)分析法 |
US9675288B2 (en) | 2013-01-29 | 2017-06-13 | Hewlett-Packard Development Company, L.P. | Apparatus having surface-enhanced spectroscopy elements on an exterior surface |
US10067060B2 (en) | 2013-01-30 | 2018-09-04 | Hewlett-Packard Development Company, L.P. | Polarization selective surface enhanced raman spectroscopy |
JP5957153B2 (ja) * | 2013-01-30 | 2016-07-27 | ヒューレット−パッカード デベロップメント カンパニー エル.ピー.Hewlett‐Packard Development Company, L.P. | 偏光選択性表面増強ラマン分光法 |
JP6294614B2 (ja) * | 2013-05-08 | 2018-03-14 | 有限会社マイテック | 癌関連物質の定量方法 |
CN103400900B (zh) * | 2013-08-08 | 2017-05-31 | 扬州大学 | ZnO量子点基深紫外传感器及制备方法 |
MY193573A (en) * | 2014-05-08 | 2022-10-19 | Mytech Co Ltd | Plasmonic chip for observing cancer related substances by localized surface plasmon resonance |
JP2017156104A (ja) * | 2016-02-29 | 2017-09-07 | 西松建設株式会社 | 光増強素子とその製造方法ならびに分光分析用キットおよび分光分析方法 |
JP6300864B2 (ja) * | 2016-08-09 | 2018-03-28 | ヒューレット−パッカード デベロップメント カンパニー エル.ピー.Hewlett‐Packard Development Company, L.P. | 外面に表面増感分光法要素を有する装置 |
US11609229B2 (en) * | 2020-04-30 | 2023-03-21 | Mytech Co. Ltd. | Fluorescence counting system for quantifying viruses or antibodies on an immobilized metal substrate by using an antigen-antibody reaction |
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