JP2018127699A - Method for synthesizing highly-dispersible silica-coated gold nanorod and dispersion liquid of synthesized gold nanorod - Google Patents
Method for synthesizing highly-dispersible silica-coated gold nanorod and dispersion liquid of synthesized gold nanorod Download PDFInfo
- Publication number
- JP2018127699A JP2018127699A JP2017022728A JP2017022728A JP2018127699A JP 2018127699 A JP2018127699 A JP 2018127699A JP 2017022728 A JP2017022728 A JP 2017022728A JP 2017022728 A JP2017022728 A JP 2017022728A JP 2018127699 A JP2018127699 A JP 2018127699A
- Authority
- JP
- Japan
- Prior art keywords
- aunr
- silicaaunr
- milliq
- absorption spectrum
- shows
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 118
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 59
- 239000006185 dispersion Substances 0.000 title claims abstract description 14
- 238000000034 method Methods 0.000 title claims description 10
- 230000002194 synthesizing effect Effects 0.000 title claims description 5
- 239000007788 liquid Substances 0.000 title claims description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 315
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims abstract description 120
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 46
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 36
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims abstract description 24
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000000576 coating method Methods 0.000 claims abstract description 21
- 239000011248 coating agent Substances 0.000 claims abstract description 20
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 20
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 31
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 229960004132 diethyl ether Drugs 0.000 abstract 1
- 238000000862 absorption spectrum Methods 0.000 description 134
- 239000000243 solution Substances 0.000 description 55
- 238000005259 measurement Methods 0.000 description 43
- 239000002904 solvent Substances 0.000 description 31
- 238000002835 absorbance Methods 0.000 description 26
- 239000007864 aqueous solution Substances 0.000 description 26
- 239000011521 glass Substances 0.000 description 21
- 238000001035 drying Methods 0.000 description 20
- 239000003960 organic solvent Substances 0.000 description 20
- 239000006228 supernatant Substances 0.000 description 20
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 18
- 239000010931 gold Substances 0.000 description 18
- 230000003287 optical effect Effects 0.000 description 17
- 238000001878 scanning electron micrograph Methods 0.000 description 16
- 239000004033 plastic Substances 0.000 description 13
- 229920003023 plastic Polymers 0.000 description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 229910052737 gold Inorganic materials 0.000 description 12
- 238000002156 mixing Methods 0.000 description 12
- 230000036962 time dependent Effects 0.000 description 12
- -1 thiol compound Chemical class 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 10
- 229960005070 ascorbic acid Drugs 0.000 description 9
- 235000010323 ascorbic acid Nutrition 0.000 description 9
- 239000011668 ascorbic acid Substances 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- 238000011481 absorbance measurement Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 230000031700 light absorption Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 238000005119 centrifugation Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002073 nanorod Substances 0.000 description 5
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 4
- 238000010790 dilution Methods 0.000 description 4
- 239000012895 dilution Substances 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 101710134784 Agnoprotein Proteins 0.000 description 3
- 239000003086 colorant Substances 0.000 description 3
- 239000003550 marker Substances 0.000 description 3
- 239000002082 metal nanoparticle Substances 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 235000005811 Viola adunca Nutrition 0.000 description 1
- 240000009038 Viola odorata Species 0.000 description 1
- 235000013487 Viola odorata Nutrition 0.000 description 1
- 235000002254 Viola papilionacea Nutrition 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000003093 cationic surfactant Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
Description
本発明は、金属ナノ微粒子の一種である金ナノロッド（以降ＡｕナノロッドあるいはＡｕＮＲとも称する）に関し、特にその表面がシリカコーティングされた金ナノロッドの合成方法及び合成された金ナノロッドの分散液に関する。 The present invention relates to a gold nanorod (hereinafter also referred to as Au nanorod or AuNR), which is a kind of metal nanoparticle, and more particularly to a method for synthesizing a gold nanorod whose surface is coated with silica and a dispersion of the synthesized gold nanorod.
金属ナノ微粒子は、局在表面プラズモン共鳴（ＬＳＰＲ）に由来する特徴的な光物性により、化学分野ばかりでなく、材料、センサ・光デバイス、バイオ、医学系など多種多様な分野での応用が期待されているナノ材料である。中でも金ナノロッドは、その異方性形状のために近年多くの分野で注目されてきている。これまでの金属ナノ微粒子研究では、調製直後の微粒子が水にのみ分散できることから、ほとんどが水溶液系に限られてきた。 Metal nanoparticles are expected to be applied not only in the chemical field but also in a wide variety of fields such as materials, sensors / optical devices, biotechnology, and medical systems due to the characteristic optical properties derived from localized surface plasmon resonance (LSPR). It is a nanomaterial. Among these, gold nanorods have attracted attention in many fields in recent years due to their anisotropic shape. In metal nanoparticle research so far, most of them have been limited to aqueous solutions because the fine particles immediately after preparation can be dispersed only in water.
その後、１９９４年にＢｒｕｓｔらがチオール化合物共存下の２層合成法が報告（非特許文献１）されて以来は、有機溶媒に可溶な金属微粒子の調製が可能となっている。その他、物理吸着系微粒子分散剤としてはポリマーや界面活性剤がしばしば使用されてはいるが、ほとんどが水溶性に限定されている。 Subsequently, since 1994 reported a two-layer synthesis method in the presence of a thiol compound (Non-patent Document 1), it has become possible to prepare metal fine particles soluble in an organic solvent. In addition, polymers and surfactants are often used as the physical adsorption type fine particle dispersant, but most of them are limited to water solubility.
また、非特許文献２のようなシリカコーティング金ナノロッドの製法が開示されている。 Moreover, the manufacturing method of the silica coating gold | metal | money nanorod like a nonpatent literature 2 is disclosed.
非特許文献１のＢｒｕｓｔらの方法で得られる微粒子界面は共有結合性でＡｕ−Ｓとなっているため、微粒子自体の性質に影響を及ぼしている可能性がある。また、非特許文献２に示された方法は、界面修飾の足場作りが目的であり、具体的な検証実験ではシリカコーティングされた金ナノロッドの形成が困難であった。したがって元来の金ナノロッドの特性を損なわずシリカコートを施した高分散性金ナノロッドの安定的な合成方法が求められていた。 Since the fine particle interface obtained by the method of Brust et al. In Non-Patent Document 1 is covalently bonded to Au—S, it may affect the properties of the fine particles themselves. The method disclosed in Non-Patent Document 2 is intended to create a scaffold for interfacial modification, and it was difficult to form a silica-coated gold nanorod in a specific verification experiment. Therefore, there has been a demand for a stable synthesis method of highly dispersible gold nanorods coated with silica without impairing the properties of the original gold nanorods.
また、シリカコートされた金ナノロッドの分散用の媒体は水にかぎられていた。 Further, the medium for dispersing the silica-coated gold nanorods was limited to water.
本発明の金ナノロッドの合成方法は、シリカコーティングされた高分散性金ナノロッドの合成方法であって、シリカコーティング時のメタノール濃度を２５±５％として金ナノロッドにシリカをコーティングする。 The method for synthesizing gold nanorods of the present invention is a method for synthesizing highly dispersed gold nanorods coated with silica, wherein the gold nanorods are coated with silica at a methanol concentration of 25 ± 5% during silica coating.
また、このシリカコーティングされた金ナノロッドを、メタノール、エタノール、ジエチルエーテル、テトラヒドロフラン、アセトン、クロロホルム、ジクロロメタン、トルエン、アセトニトリル、ＤＭＳＯの何れかの媒体にコロイド分散するようにする。 The silica-coated gold nanorods are colloidally dispersed in any medium of methanol, ethanol, diethyl ether, tetrahydrofuran, acetone, chloroform, dichloromethane, toluene, acetonitrile, DMSO.
シリカコートされた金ナノロッドの安定的な合成を可能とすることができる。また、高分散性と安定的取扱いが確保された水以外の媒体を用いた分散液を提供することが可能となる。 Stable synthesis of silica-coated gold nanorods can be enabled. In addition, it is possible to provide a dispersion using a medium other than water that ensures high dispersibility and stable handling.
以下、本発明の好適な実施の形態につき図面を用いて説明する。 Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.
図１は、本発明の金ナノロッド（ＡｕナノロッドあるいはＡｕＮＲ）の製造方法を示す図である。 FIG. 1 is a view showing a method for producing a gold nanorod (Au nanorod or AuNR) according to the present invention.
まず、初めに（ステップ１：Ｓ１）塩化金酸（ＨＡｕＣｌ４）を還元し界面活性剤を備えたＡｕ粒子（ＳｅｅｄＳｏｌｕｔｉｏｎ）を作成する。ここで、ＣＴＡＢ（臭化ヘキサデシルトリメチルアンモニウム）は陽イオン界面活性剤である。 First, first (step 1: S1), chloroauric acid (HAuCl 4 ) is reduced to prepare Au particles (Seed Solution) having a surfactant. Here, CTAB (hexadecyltrimethylammonium bromide) is a cationic surfactant.
次に（ステップ２：Ｓ２）、Ａｇ＋を用いさらに還元（Ａｓｃｏｒｂｉｃ−ａｃｉｄ）を行いＡｕ粒子を金ナノロッド化する。 Next (step 2: S2), further reducing (Ascorbic-acid) using Ag + , Au particles are converted into gold nanorods.
そして（ステップ３：Ｓ３）、金ナノロッドにシリカコーティングを実施する。ここで、シリカコーティングは２０ｖｏｌ％ＴＥＯＳ／メタノール（ＭｅＯＨ）を用いて行う。 Then (step 3: S3), silica coating is performed on the gold nanorods. Here, the silica coating is performed using 20 vol% TEOS / methanol (MeOH).
一般的に知られている、金ナノロッドのシリカコーティング時のメタノール濃度は０．９％程度で、検証実験を行ったところシリカコーティングされた金ナノロッドの形成はできなかった。そのため、諸条件を変えて試行錯誤したところ、シリカコーティング時にメタノール濃度を２５±５ｖ／ｖ％まで高めることにより常温でシリカコーティングされた金ナノロッドの形成が確認された。 In general, the methanol concentration of gold nanorods during silica coating was about 0.9%, and a verification experiment was conducted. As a result, silica-coated gold nanorods could not be formed. Therefore, when various conditions were changed and trial and error were performed, formation of silica-coated gold nanorods at room temperature was confirmed by increasing the methanol concentration to 25 ± 5 v / v% during silica coating.
一般に金ナノロッドはマーカー等に利用されるため、その基本特性として光の吸収特性が重要である。金（Ａｕ）に光を吸収させることでマーカーとしての効果を奏する。したがって、コーティングによるその劣化は問題となる。しかしながら、上述の方法により得られたシリカコーティングされたＡｕＮＲは、水溶液に高分散化した溶液においてその吸収スペクトルが金ナノロッドとシリカコーティングされた金ナノロッドとの間で遜色がないことが以下に示すように明らかとなった。つまり、シリカコートを行っても光特性はほとんど損なわないことがわかる。 Since gold nanorods are generally used for markers and the like, light absorption characteristics are important as their basic characteristics. Gold (Au) is effective as a marker by absorbing light. Therefore, its degradation due to coating becomes a problem. However, the silica-coated AuNR obtained by the above-described method shows that the absorption spectrum is not inferior between gold nanorods and silica-coated gold nanorods in a highly dispersed solution in an aqueous solution. Became clear. That is, it can be seen that the optical characteristics are hardly impaired even when silica coating is performed.
また、上述した方法により作成されたシリカコーティングされた金ナノロッドを超純水（ｍｉｌｌｉＱ）（Ｈ２Ｏ）、メタノール（ＭｅＯＨ）、エタノール（ＥｔＯＨ）、ジエチルエーテル（Ｅｔ２Ｏ）、テトラヒドロフラン（ＴＨＦ）、アセトン（Ｍｅ２ＣＯ）、クロロホルム（ＣＨＣｌ３）、ジクロロメタン（ＣＨ２Ｃｌ２）、トルエン（ＰｈＣＨ３）、ｎ−ヘキサン（Ｃ６Ｈ１４）、アセトニトリル（ＭｅＣＮ）、ジメチルスルホキシド（ＤＭＳＯ）の１２種の溶媒にて、分散性を確認した。確認は、光吸収スペクトルをみることで行った。シリカコーティングされた金ナノロッドはヘキサン以外の溶媒で赤紫色の溶液として分散できていることが初めて明らかとなった（図１２および図１４下段）。ｎ−ヘキサンを除く１１種の溶媒中のシリカコーティングされた金ナノロッドの光吸収スペクトルのピークが水溶液と同じ部分で観測された(図１３、図１５）。なお、ここでｍｉｌｌｉＱ（超純水）は、ミリポア社製超純粋製造装置で作られた超純水である。 In addition, the silica-coated gold nanorods prepared by the above-described method were used as ultrapure water (milliQ) (H 2 O), methanol (MeOH), ethanol (EtOH), diethyl ether (Et 2 O), tetrahydrofuran (THF). , Acetone (Me 2 CO), chloroform (CHCl 3 ), dichloromethane (CH 2 Cl 2 ), toluene (PhCH 3 ), n-hexane (C 6 H 14 ), acetonitrile (MeCN), dimethyl sulfoxide (DMSO) 12 Dispersibility was confirmed with a seed solvent. The confirmation was made by looking at the light absorption spectrum. It became clear for the first time that the gold nanorods coated with silica could be dispersed as a red-purple solution in a solvent other than hexane (FIG. 12 and the lower part of FIG. 14). The peaks of the light absorption spectra of silica-coated gold nanorods in 11 types of solvents except n-hexane were observed in the same part as the aqueous solution (FIGS. 13 and 15). Here, milliQ (ultra-pure water) is ultra-pure water made by an ultra-pure manufacturing apparatus manufactured by Millipore.
つまり、シリカコーティングされた金ナノロッドは水以外において、少なくともメタノール、エタノール、ジエチルエーテル、テトラヒドロフラン、アセトン、クロロホルム、ジクロロメタン、トルエン、アセトニトリル、ＤＭＳＯの何れかである媒体（溶液）に分散できる。したがってメタノール、エタノール、ジエチルエーテル、アセトン、クロロホルム、ジクロロメタン、トルエン、ＤＭＳＯ、アセトニトリル、テトラヒドロフランの何れかの媒体（溶液）にシリカコーティングされた金ナノロッドがコロイド分散した分散液が作成可能である。ここで、各媒体の純度は略１００％である。実質的には純度は９５％ｖ／ｖ％以上のものであればよい。 That is, the silica-coated gold nanorods can be dispersed in a medium (solution) that is at least one of methanol, ethanol, diethyl ether, tetrahydrofuran, acetone, chloroform, dichloromethane, toluene, acetonitrile, and DMSO, other than water. Therefore, it is possible to prepare a dispersion liquid in which gold nanorods coated with silica in a medium (solution) of methanol, ethanol, diethyl ether, acetone, chloroform, dichloromethane, toluene, DMSO, acetonitrile, or tetrahydrofuran are colloidally dispersed. Here, the purity of each medium is approximately 100%. The purity may be substantially 95% v / v% or more.
以下詳細にその内容を記す。なお、下記に示す吸収スペクトル測定結果（図２、３、５、６、９、１１、１３、１５、１７〜１９、２４、２５、２８〜３０、３５〜４５、４７，４８、５０、５１，５５、５７、５８）は、吸収スペクトルの波長（λ）（単位ｎｍ）を横軸に、吸収度（ａｂｓｏｒｂａｎｃｅ）を縦軸に表したものである。また、図４９、５２、５３、５４、５６、５９、６０は、特定の波長におけるサンプル濃度（ｍＭ）を横軸に吸光度（ａｂｓｏｒｂａｎｃｅ）を縦軸に表したものである。 The details are described below. In addition, the absorption spectrum measurement result shown below (FIG. 2, 3, 5, 6, 9, 11, 13, 15, 17-19, 24, 25, 28-30, 35-45, 47, 48, 50, 51 , 55, 57, and 58), the wavelength (λ) (unit: nm) of the absorption spectrum is shown on the horizontal axis, and the absorbance (absorbance) is shown on the vertical axis. 49, 52, 53, 54, 56, 59, and 60 show the sample concentration (mM) at a specific wavelength on the horizontal axis and the absorbance on the vertical axis.
１．金ナノロッド（ＡｕＮＲ）の合成 1. Synthesis of gold nanorods (AuNR)
１−１．種溶液（Ｓｅｅｄ ｓｏｌｕｔｉｏｎ）の作成 1-1. Preparation of seed solution
まず最初に、種溶液（Ｓｅｅｄ ｓｏｌｕｔｉｏｎ）の作成について説明する。ここは図１のステップ１（Ｓ１）に相当する。 First, preparation of a seed solution will be described. This corresponds to step 1 (S1) in FIG.
１４ｍＬ容ガラス製スナップバイアル瓶に０．１２５Ｍ‐ＣＴＡＢ（臭化ヘキサデシルトリメチルアンモニウム）水溶液８．０ｍＬ（１．０ｍｍｏｌ）を入れた。ここに、０．１Ｍ−ＫＢｒ水溶液１．０ｍＬ（０．１ｍｍｏｌ）を加え、１０回転倒混合した。更に、２．４ｍＭ−ＨＡｕＣｌ４・４Ｈ２Ｏ水溶液１．０ｍＬ（２．４μｍｏｌ：マイクロモル）を加え、１０回転倒混合した。この際、溶液は明るい黄色を呈した。この後、３０℃に維持しながらマグネチックスターラーを用いて激しく撹拌を開始した。ここに、氷冷した１０ｍＭ−ＮａＢＨ４水溶液０．６ｍＬ（６．０μｍｏｌ）を加えた。この際、溶液は薄い茶黄色を呈した。このまま撹拌を２ｍｉｎ（分）維持し、撹拌を停止させ３ｍｉｎ（分）静置した後、７回転倒混合した。これを３０℃の恒温水槽中に１ｈ（１時間）静置させた。 8.0 mL (1.0 mmol) of 0.125M-CTAB (hexadecyltrimethylammonium bromide) aqueous solution was placed in a 14 mL glass snap vial. To this, 1.0 mL (0.1 mmol) of 0.1M-KBr aqueous solution was added and mixed by inverting 10 times. Further, 1.0 mL (2.4 μmol: micromol) of 2.4 mM-HAuCl 4 .4H 2 O aqueous solution was added and mixed by inverting 10 times. At this time, the solution had a bright yellow color. Thereafter, vigorous stirring was started using a magnetic stirrer while maintaining the temperature at 30 ° C. To this, 0.6 mL (6.0 μmol) of an ice-cooled 10 mM NaBH 4 aqueous solution was added. At this time, the solution had a light brown yellow color. Stirring was maintained for 2 minutes (minutes), stirring was stopped and the mixture was allowed to stand for 3 minutes (minutes). This was allowed to stand in a constant temperature water bath at 30 ° C. for 1 h (1 hour).
この結果、総量１０．６ｍＬ、最終的なＣＴＡＢ、ＫＢｒ、ＨＡｕＣｌ４・４Ｈ２Ｏ、ＮａＢＨ４の濃度がそれぞれ、９４．３ｍＭ、９．４３ｍＭ、０．２２６ｍＭ、０．５６６ｍＭの種溶液（シードソリューション）を作成した。 As a result, the total amount was 10.6 mL, and the final CTAB, KBr, HAuCl 4 .4H 2 O, and NaBH 4 concentrations were 94.3 mM, 9.43 mM, 0.226 mM, and 0.566 mM, respectively. )created.
ここで０．１２５Ｍ−ＣＴＡＢ水溶液は、ＣＴＡＢ（０．３６４０ｇ、１．０ｍｍｏｌ）をｍｉｌｌｉＱ−８ｍＬに、０．１Ｍ−ＫＢｒ水溶液は、ＫＢｒ（１１９ｍｇ、１．０ｍｍｏｌ）をｍｉｌｌｉＱ−１０ｍＬに、２．４ｍＭ−ＨＡｕＣｌ４・４Ｈ２Ｏ水溶液は、ＨＡｕＣｌ４・４Ｈ２Ｏ（８．８ｍｇ、２１．１２μｍｏｌ）をｍｉｌｌｉＱ−８．８ｍＬにそれぞれ溶解させて作成した。これらに用いたｍｉｌｌｉＱは３０℃である。また、１０ｍＭ−ＮａＢＨ４水溶液は、ＮａＢＨ４（３７．８ｍｇ、０．１ｍｍｏｌ）をｍｉｌｌｉＱ−１ｍＬで溶解した後、ｍｉｌｌｉＱ−９ｍＬを加えた。ここから１ｍＬを別の容器に移し替え、ｍｉｌｌｉＱ−９ｍＬを加え作成した。１０ ｍＭ−ＮａＢＨ４水溶液の作成に用いたｍｉｌｌｉＱは氷冷したものを使用した。 Here, the 0.125 M-CTAB aqueous solution is CTAB (0.3640 g, 1.0 mmol) in milliQ-8 mL, and the 0.1 M-KBr aqueous solution is KBr (119 mg, 1.0 mmol) in milliQ-10 mL. The 4 mM-HAuCl 4 .4H 2 O aqueous solution was prepared by dissolving HAuCl 4 .4H 2 O (8.8 mg, 21.12 μmol) in milliQ-8.8 mL, respectively. MilliQ used for these is 30 degreeC. Further, 10 mM-NaBH 4 aqueous solution were dissolved NaBH 4 (37.8mg, 0.1mmol) with milliQ-1 mL, was added milliQ-9 mL. From here, 1 mL was transferred to another container and added with milliQ-9 mL. MilliQ used for preparation of 10 mM NaBH 4 aqueous solution was ice-cooled.
１−２．成長溶液（Ｇｒｏｗｔｈ ｓｏｌｕｔｉｏｎ）の作成 1-2. Creation of growth solution
次に成長溶液（Ｇｒｏｗｔｈ ｓｏｌｕｔｉｏｎ）の作成について説明する。ここは図１のステップ２（Ｓ２）に相当する。 Next, creation of a growth solution will be described. This corresponds to step 2 (S2) in FIG.
２００ｍＬ容ガラス製メジューム瓶に０．１２２Ｍ−ＣＴＡＢ水溶液、７７ｍＬ（９．３９４ｍｍｏｌ）を入れ、室温でマグネチックスターラーを用いて撹拌を開始した。ここに、０．９４１２Ｍ−ＫＢｒ水溶液１．０ｍＬ（０．９４１２ｍｍｏｌ）、１９．２ｍＭＡｇＮＯ３水溶液１．０ ｍＬ（１９．２μｍｏｌ）、４．６ｍＭ−ＨＡｕＣｌ４・４Ｈ２Ｏ水溶液、２０ｍＬ（９２．０μｍｏｌ）の順に加えた後、溶液は明るい黄色を呈した。次に、０．１０５Ｍ−ＡＡ（アスコルビン酸）水溶液（ＡＡ１と称する）１．０ｍＬ（０．１０５ｍｍｏｌ）を加えることで、溶液は無色透明に変化した。更に、恒温水槽中に１ｈ（１時間）静置させたＳｅｅｄ−ｓｏｌｕｔｉｏｎ０．１３５ｍＬ加え、マグネチックスターラーの撹拌速度を上げた。ここに、９．４８ｍＭ−ＡＡ（アスコルビン酸）水溶液（ＡＡ２と称する）５．０ｍＬ（４７．４μｍｏｌ）を１０ｍｉｎ（分）毎に３００μＬずつ（最後のみ２００μＬ）加えた。加え終わった後、１０ｍｉｎ（分）撹拌を維持した。これを成長溶液（Ｇｒｏｗｔｈ ｓｏｌｕｔｉｏｎ）、すなわちＡｕＮＲ（Ａｕ ｎａｎｏｒｏｄｓ／金ナノロッド）溶液とした。 A 0.122M-CTAB aqueous solution, 77 mL (9.394 mmol) was placed in a 200 mL glass medium bottle, and stirring was started at room temperature using a magnetic stirrer. Here, 1.0 mL (0.9412 mmol) of 0.9412M-KBr aqueous solution, 1.0 mL (19.2 μmol) of 19.2 mM AgNO 3 aqueous solution, 20 mL (92.0 μmol) of 4.6 mM-HAuCl 4 .4H 2 O aqueous solution ) In order, the solution had a bright yellow color. Next, by adding 1.0 mL (0.105 mmol) of an aqueous 0.105M-AA (ascorbic acid) solution (referred to as AA1), the solution turned colorless and transparent. Furthermore, 0.135 mL of Seed-solution which was allowed to stand for 1 h (1 hour) in a constant temperature water bath was added, and the stirring speed of the magnetic stirrer was increased. To this was added 5.0 mL (47.4 μmol) of a 9.48 mM-AA (ascorbic acid) aqueous solution (referred to as AA2) at a rate of 300 μL every 10 min (minute) (200 μL only at the end). After the addition was complete, stirring was maintained for 10 min (min). This was used as a growth solution, that is, an AuNR (Au nanorods / gold nanorod) solution.
この成長溶液は、総量１０５．１３５ｍＬ、最終的なＣＴＡＢ、ＫＢｒ、ＡｇＮＯ３、ＨＡｕＣｌ４・４Ｈ２Ｏ、ＡＡ１、Ａｕｓｅｅｄ、ＡＡ２、金原子の各濃度がそれぞれ８９．４ｍＭ、８．９５ｍＭ、０．１８３ｍＭ、０．８７５ｍＭ、０．９９９ｍＭ、０．２９１ｎＭ、０．４５１ｍＭ、０．８８ｍＭであった。 This growth solution has a total amount of 105.135 mL, and final concentrations of CTAB, KBr, AgNO 3 , HAuCl 4 .4H 2 O, AA1, Aused, AA2, and gold atoms are 89.4 mM, 8.95 mM, and 0.8, respectively. It was 183 mM, 0.875 mM, 0.999 mM, 0.291 nM, 0.451 mM, 0.88 mM.
ここで得られた金原子濃度０．８８ｍＭのＡｕＮＲの吸収スペクトル測定を合成直後（０ｈ／０時間）と２４ｈ（２４時間）後の２回行った。ＡｕＮＲの吸収スペクトル測定の測定結果を図２に示す。図２において実線は０ｈ（０時間）、点線は２４ｈ（２４時間）後のＡｕＮＲの吸収スペクトルである。縦軸（ｌｏｎｇｉｔｕｄｉｎａｌ）は吸光度（ａｂｓｏｒｂａｎｃｅ）であり、横軸は波長（ｎｍ）である。図２に示すように０ｈ（０時間）後のＡｕＮＲの吸収スペクトでは波長７４４ｎｍで吸光度が極大値（ここでは最大値でもある）を、２４ｈ（２４時間）後のＡｕＮＲの吸収スペクトルでは波長７３８ｎｍで吸光度が極大値（ここでは最大値でもある）を示した。０ｈ（０時間）後のＡｕＮＲの吸収スペクトではλｍａｘ＝７４４ｎｍ、２４ｈ（２４時間）後のＡｕＮＲの吸収スペクトルではλｍａｘ＝７３８ｎｍであり、ほぼ同じである。なお、光路長１ｃｍのＰＭＭＡセルを使用し、ｍｉｌｌｉＱで１０倍希釈をしたＡｕＮＲ溶液を測定した。これ以降、本明細書では吸収スペクトルにおいて吸光度が極大値をとる波長をλｍａｘと称する。 The absorption spectrum of the AuNR having a gold atom concentration of 0.88 mM obtained here was measured twice immediately after synthesis (0 h / 0 hour) and after 24 h (24 hours). The measurement result of the absorption spectrum measurement of AuNR is shown in FIG. In FIG. 2, the solid line is the absorption spectrum of AuNR after 0 h (0 hour) and the dotted line is 24 h (24 hours). The vertical axis (longitudinal) is absorbance (absorbance), and the horizontal axis is wavelength (nm). As shown in FIG. 2, the absorption spectrum of AuNR after 0 h (0 hours) shows a maximum absorbance (here also the maximum value) at a wavelength of 744 nm, and the absorption spectrum of AuNR after 24 h (24 hours) shows a wavelength of 738 nm. Absorbance showed a maximum value (here also the maximum value). In the absorption spectrum of AuNR after 0 h (0 hour), λmax = 744 nm, and in the absorption spectrum of AuNR after 24 h (24 hours), λmax = 738 nm, which is almost the same. An AuNR solution diluted 10 times with milliQ was measured using a PMMA cell with an optical path length of 1 cm. Hereinafter, in this specification, the wavelength at which the absorbance reaches the maximum value in the absorption spectrum is referred to as λmax.
なお、ここで０．１２２Ｍ−ＣＴＡＢ水溶液はＣＴＡＢ（３．４３０９ｇ、９．３９ｍｍｏｌ）をｍｉｌｌｉＱ−７７ｍＬに、０．９４１２Ｍ−ＫＢｒ水溶液は、ＫＢｒ（１．１２ｇ、９．４１ｍｍｏｌ）をｍｉｌｌｉＱ−１０ｍＬに、１９．２ｍＭ−ＡｇＮＯ３水溶液は、ＡｇＮＯ３（３２．６ｍｇ、０．１９２ｍｍｏｌ）をｍｉｌｌｉＱ−１０ｍＬに、４．６ｍＭ−ＨＡｕＣｌ４・４Ｈ２Ｏ水溶液は、ＨＡｕＣｌ４・４Ｈ２Ｏ（４７．９５ｍｇ、０．１１６ｍｍｏｌ）をｍｉｌｌｉＱ−２５．３ｍＬに、０．１０５Ｍ−ＡＡ（アスコルビン酸）水溶液は、ＡＡ（アスコルビン酸）（１８６ｍｇ、１．０５ｍｍｏｌ）をｍｉｌｌｉＱ−１０ｍＬに、９．４８ｍＭ−ＡＡ水溶液は、ＡＡ（アスコルビン酸）（１６．７ｍｇ、９７．８ｍｍｏｌ）をｍｉｌｌｉＱ−１０ｍＬに、それぞれ溶解させて作成した。なお、ここで用いたｍｉｌｌｉＱはいずれも３０℃である。 Here, the 0.122M-CTAB aqueous solution is CTAB (3.4309 g, 9.39 mmol) to milliQ-77 mL, and the 0.9412 M-KBr aqueous solution is KBr (1.12 g, 9.41 mmol) to milliQ-10 mL. 19.2 mM-AgNO 3 aqueous solution is AgNO 3 (32.6 mg, 0.192 mmol) to milliQ-10 mL, and 4.6 mM-HAuCl 4 .4H 2 O aqueous solution is HAuCl 4 .4H 2 O (47.95 mg). 0.116 mmol) to milliQ-25.3 mL, 0.105 M-AA (ascorbic acid) aqueous solution to AA (ascorbic acid) (186 mg, 1.05 mmol) to milliQ-10 mL, and 9.48 mM-AA aqueous solution to , AA (ascorbic acid) (16.7 mg, 97.8 m The ol) in milliQ-10 mL, was prepared by dissolving, respectively. In addition, all milliQ used here is 30 degreeC.
１−３．成長溶液（Ｇｒｏｗｔｈ ｓｏｌｕｔｉｏｎ）の精製 1-3. Purification of growth solution (Growth solution)
２４ｈ後、ＡｕＮＲ溶液を５０ｍＬ容プラスチック製遠心管に２６ｍＬずつ分け取り、これを４本作製した（全量１０４ｍＬ）。これを遠心分離（６０００ｒｐｍ［３５４２×ｇ：ここでｇは重力加速度］、１２０ｍｉｎ(分）、２５℃）し、この後、上清を除き、同量（約２６ｍＬ）のｍｉｌｌｉＱでそれぞれ再分散をした。精製された４本のＡｕＮＲ溶液を新しい２００ｍＬ容ガラス製メジューム瓶に移し替え、まとめたＡｕＮＲの吸収スペクトル測定を行った（図３）。図３に示すように精製されたＡｕＮＲの吸収スペクトル（実線）においては波長７４１ｎｍで吸光度が極大値（ここでは最大値でもある）を示した（λｍａｘ＝７４１ｎｍ）。また同図に２４ｈ（２４時間）後のＡｕＮＲの吸収スペクト(点線）を比較のため示す。測定条件は上記（１−２項）と同様におこなった。ここで図３におけるＡｕＮＲ合成２４ｈ後の吸光度の極大値、すなわち波長７３８ｎｍの吸光度（Ａｂｓ７３８と記す）から求められた再分散率（Ａｂｓ７３８における再分散率）は、１００．９％（０．５３５３７／０．５３０４８７×１００＝１００．９％）であった。 After 24 hours, 26 mL of the AuNR solution was divided into 50 mL plastic centrifuge tubes, and four of these were prepared (total volume 104 mL). This was centrifuged (6000 rpm [3542 × g: where g is gravitational acceleration], 120 min (min), 25 ° C.), and then the supernatant was removed and redispersed with the same amount (about 26 mL) of milliQ. did. The four purified AuNR solutions were transferred to a new 200 mL glass medium bottle, and the combined absorption spectra of AuNR were measured (FIG. 3). As shown in FIG. 3, in the absorption spectrum (solid line) of the purified AuNR, the absorbance showed a maximum value (here also the maximum value) at a wavelength of 741 nm (λmax = 741 nm). In addition, the absorption spectrum (dotted line) of AuNR after 24 h (24 hours) is shown in FIG. The measurement conditions were the same as in (1-2) above. Here, the maximum value of the absorbance after AuNR synthesis 24h in FIG. 3, that is, the redispersion rate (redispersion rate in Abs738) obtained from the absorbance at 738 nm (referred to as Abs738) is 100.9% (0.53537 / 0.530487 × 100 = 100.9%).
精製したＡｕＮＲの走査型電子顕微鏡（Ｓｃａｎｎｉｎｇ Ｅｌｅｃｔｒｏｎ Ｍｉｃｒｏｓｃｏｐｅ：ＳＥＭ）観察を行った（図４）。図４に示すＳＥＭ像で観察されたＡｕＮＲは、長軸方向に５３．１±５．２ｎｍ、短軸方向に１７．８±２．３ｎｍ、アスペクト比が３．０±０．５であった。このように作成されたＡｕＮＲは、球ではなく、長軸／短軸比（アスペクト比）が３．０程度であるような細長い形状を持つため、後述するように吸光スペクトル解析において、長軸方向、短軸方向に由来したスペクトル成分を備えることとなる。 The purified AuNR was observed with a scanning electron microscope (SEM) (FIG. 4). The AuNR observed in the SEM image shown in FIG. 4 was 53.1 ± 5.2 nm in the major axis direction, 17.8 ± 2.3 nm in the minor axis direction, and the aspect ratio was 3.0 ± 0.5. . Since the AuNR created in this way is not a sphere but has a long and narrow shape with a major axis / minor axis ratio (aspect ratio) of about 3.0, the major axis direction is used in the absorption spectrum analysis as will be described later. The spectral component derived from the minor axis direction is provided.
このＡｕＮＲ溶液を用いてシリカコーティングを行った。 Silica coating was performed using this AuNR solution.
２．ＡｕＮＲのシリカコーティング 2. AuNR silica coating
続いてＡｕＮＲのシリカコーティングについて説明する。ここは図１のステップ３（Ｓ３）に相当する。 Next, the AuNR silica coating will be described. This corresponds to step 3 (S3) in FIG.
２−１．ＳｉｌｉｃａＡｕＮＲ溶液の作成 2-1. Preparation of SilicaAuNR solution
上述のようにして作成されたＡｕＮＲ溶液のＡｕＮＲにシリカコーティングを行った。上述したＡｕＮＲ溶液を５０ｍＬ容プラスチック製遠心管に１５ｍＬずつ分け、これを２本作製した（全量３０ｍＬ）。これを遠心分離（６０００ｒｐｍ［３５４２×ｇ］、６０ｍｉｎ(分）、２５℃）し、この後、上清を３．７５ｍＬ除き、３．７５ｍＬのＭｅＯＨ（メタノール）でそれぞれ再分散することで、ＡｕＮＲ／２５％ＭｅＯＨａｑ．を作製した。この２本のＡｕＮＲ／２５％ＭｅＯＨａｑ．を新しい５０ｍＬ容プラスチック製広口瓶に移し替え、まとめたＡｕＮＲ／２５％ＭｅＯＨａｑ．（全量３０ｍＬ）の吸収スペクトル測定を行った（図５）。図５に示すようにＡｕＮＲ／２５％ＭｅＯＨａｑ．の吸収スペクトル（実線）においては波長７３６．５ｎｍで吸光度が極大値（ここでは最大値でもある）を示した。精製されたＡｕＮＲの吸収スペクトル（点線）は比較のため示している。測定条件は上記（１−２項、１−３項）と同様に行った。また、この時点での波長７４１ｎｍの吸光度（Ａｂｓ７４１と記す）から求められた再分散率（Ａｂｓ７４１における再分散率）は９７．６％（０．５２２３８５／０．５３５３７×１００＝９７．６％）となった。 Silica coating was applied to AuNR of the AuNR solution prepared as described above. The above AuNR solution was divided into 15 mL portions into 50 mL plastic centrifuge tubes, and two of them were prepared (total amount 30 mL). This was centrifuged (6000 rpm [3542 × g], 60 min (min), 25 ° C.), and thereafter, 3.75 mL of the supernatant was removed and redispersed with 3.75 mL of MeOH (methanol). / 25% MeOHaq. Was made. These two AuNR / 25% MeOHaq. Was transferred to a new 50 mL plastic jar and the combined AuNR / 25% MeOHaq. The absorption spectrum of (total amount 30 mL) was measured (FIG. 5). As shown in FIG. 5, AuNR / 25% MeOHaq. In the absorption spectrum (solid line), the absorbance showed a maximum value (here, also the maximum value) at a wavelength of 736.5 nm. The absorption spectrum (dotted line) of the purified AuNR is shown for comparison. The measurement conditions were the same as those described above (1-2, 1-3). In addition, the redispersion rate (redispersion rate in Abs741) obtained from the absorbance at 741 nm (denoted as Abs741) at this time is 97.6% (0.522385 / 0.53537 × 100 = 97.6%). It became.
５０ｍＬ容プラスチック製広口瓶に入れたＡｕＮＲ／２５％ＭｅＯＨａｑ．（全量３０ｍＬ）を室温でマグネチックスターラーを用いて撹拌を開始し、０．１Ｍ−ＮａＯＨ水溶液３００μＬ（３０μｍｏｌ）を加えた。ここに、２０ｖｏｌ％ＴＥＯＳ／ＭｅＯＨを３０ｍｉｎ（分）毎に９０μＬを３回加えた後（合計２７０μＬ、０．２４１ｍｍｏｌ）、約１０ｍｉｎ（分）撹拌を維持し停止した。これを２５℃に設定されたインキュベーターで２４ｈ（２４時間）静置保存した。これをシリカコーティングＡｕＮＲ溶液（ＳｉｌｉｃａＡｕＮＲ溶液）とした。 AuNR / 25% MeOHaq. In a 50 mL plastic jar. (Total volume 30 mL) was stirred at room temperature using a magnetic stirrer, and 0.1 M NaOH aqueous solution 300 μL (30 μmol) was added. Here, 90 μL of 20 vol% TEOS / MeOH was added three times every 30 min (min) (total 270 μL, 0.241 mmol), and then stirring was maintained for about 10 min (min) and stopped. This was stored still for 24 hours (24 hours) in an incubator set at 25 ° C. This was used as a silica-coated AuNR solution (SilicaAuNR solution).
ここで、０．１Ｍ−ＮａＯＨ水溶液は、ＮａＯＨ（９６．３ｇ、２．４ｍｍｏｌ）をｍｉｌｌｉＱ−２４ｍＬに溶解させて作成し、２０ｖｏｌ％ＴＥＯＳメタノール溶液（０．８９４Ｍ、０．８９４ｍｍｏｌ）は、ＴＥＯＳ０．２ｍＬをＭｅＯＨ０．８ｍＬに溶解させて作成した。 Here, 0.1 M NaOH aqueous solution was prepared by dissolving NaOH (96.3 g, 2.4 mmol) in milliQ-24 mL, and 20 vol% TEOS methanol solution (0.894 M, 0.894 mmol) It was prepared by dissolving 2 mL in MeOH 0.8 mL.
また、作成されたシリカコーティングＡｕＮＲ溶液は、総量３０．５７ｍＬ、ＮａＯＨ、ＴＥＯＳ、金原子の濃度はそれぞれ０．９８ｍＭ、７．９０ｍＭ、０．８６ｍＭであった。ここで、作成されたシリカコーティングＡｕＮＲ溶液の大半は当初のＡｕＮＲ／２５％ＭｅＯＨａｑ．であるため、シリカコーティングＡｕＮＲ溶液のメタノールの濃度は実質的に２５±５ｖ／ｖ％とほぼ等価である。 The prepared silica-coated AuNR solution had a total amount of 30.57 mL, and the concentrations of NaOH, TEOS, and gold atoms were 0.98 mM, 7.90 mM, and 0.86 mM, respectively. Here, most of the prepared silica-coated AuNR solution is the original AuNR / 25% MeOHaq. Therefore, the concentration of methanol in the silica-coated AuNR solution is substantially equivalent to 25 ± 5 v / v%.
２−２．ＳｉｌｉｃａＡｕＮＲ溶液の精製
ＳｉｌｉｃａＡｕＮＲ溶液作成から２４ｈ（２４時間）後、ＳｉｌｉｃａＡｕＮＲ溶液を５０ｍＬ容プラスチック製遠心管に１５ｍＬずつ分け取り、これを２本作製した（全量３０ｍＬ）。これを遠心分離（６０００ｒｐｍ［３５４２×ｇ］、６０ｍｉｎ（分）、２５℃）し、上清を除き、同量（約１５ｍＬ）のＭｅＯＨでそれぞれ再分散をした。更に、これを遠心分離（４５００ｒｐｍ［１９９２×ｇ］、３０ｍｉｎ（分）、２５℃）し、上清を除き、同量（約１５ｍＬ）のＭｅＯＨでそれぞれ再分散をした．この２本のＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨを新しい５０ｍＬ容プラスチック製広口瓶に移し替え、まとめたＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨ（全量３０ｍＬ）の吸収スペクトル測定を行った（図６）。図６に示すようにＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの吸収スペクトル（実線）においては波長７３３ｎｍで吸光度が極大値（ここでは最大値でもある）を示した（λｍａｘ＝７３３ｎｍ）。ＡｕＮＲ／２５％ＭｅＯＨａｑ．の吸収スペクトル（点線）は比較のため示している。なお、測定は、光路長１ｃｍのガラスセルを使用し、ＭｅＯＨで１０倍希釈をしたＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨを測定した。また、この時点での波長７３６．５ｎｍの吸光度（Ａｂｓ７３６．５）から求められた再分散率（Ａｂｓ７３６．５における再分散率）は７３．１％（０．３９１４７９／０．５３５３７×１００＝７３．１％）であった。
2-2. Purification of SilicaAuNR solution 24 hours (24 hours) after the preparation of the SilicaAuNR solution, the SilicaAuNR solution was divided into 15 mL portions into 50 mL plastic centrifuge tubes, and two of them were prepared (total volume 30 mL). This was centrifuged (6000 rpm [3542 × g], 60 min (min), 25 ° C.), the supernatant was removed, and each was redispersed with the same amount (about 15 mL) of MeOH. Further, this was centrifuged (4500 rpm [1992 × g], 30 min (min), 25 ° C.), the supernatant was removed, and each was redispersed with the same amount (about 15 mL) of MeOH. These two SilicaAuNR / MeOH were transferred to a new 50 mL plastic wide-mouth bottle, and the absorption spectra of the collected SilicaAuNR / MeOH (total amount 30 mL) were measured (FIG. 6). As shown in FIG. 6, in the absorption spectrum (solid line) of SilicaAuNR / MeOH, the absorbance showed a maximum value (here also the maximum value) at a wavelength of 733 nm (λmax = 733 nm). AuNR / 25% MeOHaq. The absorption spectrum (dotted line) is shown for comparison. The measurement was performed using a glass cell having an optical path length of 1 cm and SilicaAuNR / MeOH diluted 10-fold with MeOH. In addition, the redispersion rate (redispersion rate in Abs736.5) obtained from the absorbance (Abs736.5) at the wavelength of 736.5 nm at this time is 73.1% (0.391479 / 0.53537 × 100 = 73). 0.1%).
次に、精製したＳｉｌｉｃａＡｕＮＲのＳＥＭ観察を行った。ＳＥＭ観察結果を図７に示す。 Next, SEM observation of the purified SilicaAuNR was performed. The SEM observation result is shown in FIG.
続けてこのようにして得られたＡｕＮＲならびにＳｉｌｉｃａＡｕＮＲについてその特性を実験により検証した。以降、ＳＥＭ像で確認されるシリカ層の厚さが２０．６±１．７ｎｍのＳｉｌｉｃａＡｕＮＲを用いて実験を行った。 Subsequently, the characteristics of the thus obtained AuNR and SilicaAuNR were verified by experiments. Thereafter, experiments were performed using SilicaAuNR having a silica layer thickness of 20.6 ± 1.7 nm confirmed by an SEM image.
３．ＳｉｌｉｃａＡｕＮＲの溶解性 3. Silica AuNR solubility
続いてＡｕＮＲおよびＳｉｌｉｃａＡｕＮＲそれぞれについて水及び有機溶媒への溶解性を検討した。本実験に用いた溶媒は、水（ｍｉｌｌｉＱ）（Ｈ２Ｏ）、メタノール（ＭｅＯＨ）、エタノール（ＥｔＯＨ）、ジエチルエーテル（Ｅｔ２Ｏ）、テトラヒドロフラン（ＴＨＦ）、アセトン（Ｍｅ２ＣＯ）、クロロホルム（ＣＨＣｌ３）、ジクロロメタン（ＣＨ２Ｃｌ２）、トルエン（ＰｈＣＨ３）、ｎ−ヘキサン（Ｃ６Ｈ１４）、アセトニトリル（ＭｅＣＮ）、ジメチルスルホキシド（ＤＭＳＯ）の１２種を用いた。 Subsequently, the solubility of water and organic solvents for each of AuNR and SilicaAuNR was examined. Solvents used in this experiment were water (milliQ) (H 2 O), methanol (MeOH), ethanol (EtOH), diethyl ether (Et 2 O), tetrahydrofuran (THF), acetone (Me 2 CO), chloroform ( Twelve kinds of CHCl 3 ), dichloromethane (CH 2 Cl 2 ), toluene (PhCH 3 ), n-hexane (C 6 H 14 ), acetonitrile (MeCN), and dimethyl sulfoxide (DMSO) were used.
３−１．ＡｕＮＲ／ｍｉｌｌｉＱの溶解性 3-1. Solubility of AuNR / milliQ
ＡｕＮＲ／ｍｉｌｌｉＱを１．５ｍＬ容エッペンドルフチューブに１．０ｍＬずつ分け、１２本作製した。これを遠心分離（４０００ｒｐｍ［１４４９×ｇ］、３０ｍｉｎ（分）、２５℃）した後、上清を除き、同量（約１．０ｍＬ）の上記の１２種類の溶媒（Ｈ２Ｏ、ＭｅＯＨ、ＥｔＯＨ、Ｅｔ２Ｏ、ＴＨＦ、Ｍｅ２ＣＯ、ＣＨＣｌ３、ＣＨ２Ｃｌ２、ＰｈＣＨ３、Ｃ６Ｈ１４、ＭｅＣＮ、ＤＭＳＯ）でそれぞれ再分散をした。再分散したＡｕＮＲ溶液をそれぞれ新しい２．２ｍＬ容ガラス製スナップバイアル瓶に移し替え、（０ｈ（０時間）の写真を図８、２４ｈ（２４時間）後の写真を図１０）吸収スペクトル測定を再分散直後（０ｈ：０時間）（図９）と２４ｈ（２４時間）後（図１１）に２回行った。２４ｈ後のＡｕＮＲ溶液は、超音波を１０ｓ（秒）照射し転倒混合を１０回した後、吸収スペクトル測定を行った。なお、測定は、光路長１ｃｍのガラスセルを使用し、各分散溶媒で１０倍希釈をしたものを測定した。 Twelve AuNR / milliQ were prepared by dividing 1.0 mL into 1.5 mL Eppendorf tubes. After centrifugation (4000 rpm [1449 × g], 30 min (min), 25 ° C.), the supernatant was removed, and the same amount (about 1.0 mL) of the above-mentioned 12 solvents (H 2 O, MeOH, EtOH, Et 2 O, THF, Me 2 CO, CHCl 3 , CH 2 Cl 2 , PhCH 3 , C 6 H 14 , MeCN, DMSO). The re-dispersed AuNR solution was transferred to a new 2.2 mL glass snap vial. (Photo of 0h (0 hour) is shown in Fig. 8, Photo after 24h (24 hours) is Fig. 10). Immediately after the dispersion (0 h: 0 hour) (FIG. 9) and 24 h (24 hours) later (FIG. 11), it was performed twice. The AuNR solution after 24 hours was irradiated with ultrasonic waves for 10 s (seconds) and subjected to inversion mixing 10 times, and then the absorption spectrum was measured. The measurement was performed using a glass cell having an optical path length of 1 cm and diluted 10-fold with each dispersion solvent.
図８は０ｈにおける水及び有機溶媒に分散させたＡｕＮＲの溶液の状態を示す図である。ＡｕＮＲは、０ｈ時点でＨ２Ｏ、ＭｅＯＨ、ＥｔＯＨ、ＴＨＦ、Ｍｅ２ＣＯ、ＭｅＣＮ、ＤＭＳＯの各溶媒ではそれぞれ赤紫、青黒、青黒、青黒、青黒、青黒、赤紫の色を呈した。一方、Ｅｔ２Ｏ、ＣＨＣｌ３、ＣＨ２Ｃｌ２、ＰｈＣＨ３、Ｃ６Ｈ１４では沈殿を生じた。そのため、吸収スペクトル測定はＨ２Ｏ、ＭｅＯＨ、ＥｔＯＨ、ＴＨＦ、Ｍｅ２ＣＯ、ＭｅＣＮ、ＤＭＳＯの各溶媒に対して行った。０ｈにおける水及び有機溶媒でのＡｕＮＲの吸収スペクトルの測定結果を図９に示す。 FIG. 8 is a view showing a state of a solution of AuNR dispersed in water and an organic solvent at 0 h. AuNR exhibited reddish purple, blue-black, blue-black, blue-black, blue-black, blue-black, and red-purple colors in each solvent of H 2 O, MeOH, EtOH, THF, Me 2 CO, MeCN, and DMSO at 0 h. On the other hand, precipitation occurred in Et 2 O, CHCl 3 , CH 2 Cl 2 , PhCH 3 , and C 6 H 14 . Therefore, absorption spectrum measurement was performed with respect to each solvent of H 2 O, MeOH, EtOH, THF, Me 2 CO, MeCN, and DMSO. The measurement results of the absorption spectrum of AuNR in water and an organic solvent at 0 h are shown in FIG.
図１０の上段は２４ｈ後における転倒混合前の水及び有機溶媒でのＡｕＮＲの溶液の状態を示している。ＡｕＮＲは２４ｈ後の転倒混合前には、Ｈ２Ｏ、Ｍｅ２ＣＯ、ＭｅＣＮ、ＤＭＳＯの各溶媒ではそれぞれ赤紫、青黒、青黒、赤紫の色を呈した。一方、ＭｅＯＨ、ＥｔＯＨ、Ｅｔ２Ｏ、ＴＨＦ、ＣＨＣｌ３、ＣＨ２Ｃｌ２、ＰｈＣＨ３、Ｃ６Ｈ１４の各溶媒では沈殿を生じた。 The upper part of FIG. 10 shows the state of the AuNR solution in water and an organic solvent before inversion mixing after 24 hours. AuNR exhibited red-purple, blue-black, blue-black, and red-purple colors in H 2 O, Me 2 CO, MeCN, and DMSO solvents before inversion mixing after 24 hours. On the other hand, precipitation occurred in each solvent of MeOH, EtOH, Et 2 O, THF, CHCl 3 , CH 2 Cl 2 , PhCH 3, and C 6 H 14 .
また、図１０の下段は超音波照射し転倒混合後（下段）の水及び有機溶媒でのＡｕＮＲの溶液の状態を示している。超音波照射後さらに転倒混合すると、Ｈ２Ｏ、ＭｅＯＨ、ＥｔＯＨ、Ｅｔ２Ｏ、ＴＨＦ、Ｍｅ２ＣＯ、ＣＨＣｌ３、ＣＨ２Ｃｌ２、ＰｈＣＨ３、ＭｅＣＮ、ＤＭＳＯの各溶媒ではそれぞれ赤紫、青黒、青黒、濃青、青黒、青黒、青黒、青黒、青紫、青黒、赤紫の色を呈したが、Ｃ６Ｈ１４の溶媒では沈殿を生じた。また、Ｃ６Ｈ１４に加えＥｔ２Ｏ、ＣＨＣｌ３、ＣＨ２Ｃｌ２、ＰｈＣＨ３の各溶媒でも転倒混合後すぐに沈殿を生じた。そのため、吸収スペクトル測定はＨ２Ｏ、ＭｅＯＨ、ＥｔＯＨ、ＴＨＦ、Ｍｅ２ＣＯ、ＭｅＣＮ、ＤＭＳＯの各溶媒に対して行った。２４ｈ後における水及び有機溶媒でのＡｕＮＲの吸収スペクトルの測定結果を図１１に示す。図９および図１１に示すようにＨ２Ｏ、ＤＭＳＯを除いては吸光スペクトルに明確な極大値を示さないことからＡｕＮＲは分散されていないことがわかる。 The lower part of FIG. 10 shows the state of the AuNR solution in water and an organic solvent after ultrasonic irradiation and inversion mixing (lower part). When further mixed by inversion after ultrasonic irradiation, red, purple and blue black are used in each solvent of H 2 O, MeOH, EtOH, Et 2 O, THF, Me 2 CO, CHCl 3 , CH 2 Cl 2 , PhCH 3 , MeCN, and DMSO, respectively. , Blue-black, dark blue, blue-black, blue-black, blue-black, blue-black, blue-violet, blue-black, red-purple, but a C 6 H 14 solvent caused precipitation. In addition to C 6 H 14 , Et 2 O, CHCl 3 , CH 2 Cl 2 , and PhCH 3 were also precipitated immediately after inversion mixing. Therefore, absorption spectrum measurement was performed with respect to each solvent of H 2 O, MeOH, EtOH, THF, Me 2 CO, MeCN, and DMSO. FIG. 11 shows the measurement results of the absorption spectrum of AuNR in water and an organic solvent after 24 hours. As shown in FIG. 9 and FIG. 11, it can be seen that AuNR is not dispersed since the absorption spectrum does not show a clear maximum value except for H 2 O and DMSO.
３−２．ＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの溶解性 3-2. Solubility of SilicaAuNR / MeOH
ＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨを１．５ｍＬ容エッペンドルフチューブに１．０ｍＬずつ分け、１２本作製した。これを遠心分離（４０００ｒｐｍ［１４４９×ｇ］、３０ｍｉｎ(分）、２５℃）した後、上清を除き、同量（約１．０ｍＬ）の上記の１２種類の溶媒（Ｈ２Ｏ、ＭｅＯＨ、ＥｔＯＨ、Ｅｔ２Ｏ、ＴＨＦ、Ｍｅ２ＣＯ、ＣＨＣｌ３、ＣＨ２Ｃｌ２、ＰｈＣＨ３、Ｃ６Ｈ１４、ＭｅＣＮ、ＤＭＳＯ）でそれぞれ再分散をした。再分散したＳｉｌｉｃａＡｕＮＲをそれぞれ新しい２．２ｍＬ容ガラス製スナップバイアル瓶に移し替え、（０ｈの写真を図１２、２４ｈ後の写真を図１４）吸収スペクトル測定を再分散直後（０ｈ）（図１３）と２４ｈ後（図１５）に２回行った。なお、測定は、光路長１ｃｍのガラスセルを使用し、各分散溶媒で１０倍希釈をしたものを測定した。 SilicaAuNR / MeOH was divided into 1.0 mL aliquots in 1.5 mL Eppendorf tubes to prepare 12 pieces. After centrifugation (4000 rpm [1449 × g], 30 min (min), 25 ° C.), the supernatant was removed, and the same amount (about 1.0 mL) of the above-mentioned 12 solvents (H 2 O, MeOH, EtOH, Et 2 O, THF, Me 2 CO, CHCl 3 , CH 2 Cl 2 , PhCH 3 , C 6 H 14 , MeCN, DMSO). Each redispersed SilicaAuNR was transferred to a new 2.2 mL glass snap vial (0h photo is shown in FIG. 12, 24h later photo is shown in FIG. 14). Absorption spectrum measurement was performed immediately after redispersion (0h) (FIG. 13). And 24 hours later (FIG. 15). The measurement was performed using a glass cell having an optical path length of 1 cm and diluted 10-fold with each dispersion solvent.
図１２は０ｈにおける水及び有機溶媒に分散させたＳｉｌｉｃａＡｕＮＲの溶液の状態を示す図である。ＳｉｌｉｃａＡｕＮＲは、０ｈ時点でＨ２Ｏ、ＭｅＯＨ、ＥｔＯＨ、Ｅｔ２Ｏ、ＴＨＦ、Ｍｅ２ＣＯ、ＣＨＣｌ３、ＣＨ２Ｃｌ２、ＰｈＣＨ３、ＭｅＣＮ、ＤＭＳＯの各溶媒すべてで赤紫の色を呈した。なおＣ６Ｈ１４の溶媒では沈殿を生じ無色であった。そのため、吸収スペクトル測定はＣ６Ｈ１４の溶媒を除く１１種の溶媒について行った。０ｈにおける水及び有機溶媒でのＳｉｌｉｃａＡｕＮＲの吸収スペクトルの測定結果を図１３に示す。 FIG. 12 is a diagram showing a state of a solution of SilicaAuNR dispersed in water and an organic solvent at 0 h. SilicaAuNR exhibited a magenta color in all the solvents H 2 O, MeOH, EtOH, Et 2 O, THF, Me 2 CO, CHCl 3 , CH 2 Cl 2 , PhCH 3 , MeCN and DMSO at 0 h. . The C 6 H 14 solvent was precipitated and was colorless. Therefore, the absorption spectrum measurement was performed for 11 types of solvents excluding the C 6 H 14 solvent. The measurement results of the absorption spectrum of SilicaAuNR in water and an organic solvent at 0 h are shown in FIG.
図１４は２４ｈ後における転倒混合前（上段）と超音波照射し転倒混合後（下段）の水及び有機溶媒でのＳｉｌｉｃａＡｕＮＲの溶液の状態を示す図である。ＳｉｌｉｃａＡｕＮＲは２４ｈ後の転倒混合前（図１４上段）には、Ｈ２Ｏ、ＭｅＯＨ、ＥｔＯＨ、Ｅｔ２Ｏ、ＴＨＦ、Ｍｅ２ＣＯ、ＣＨＣｌ３、ＣＨ２Ｃｌ２、ＭｅＣＮ、ＤＭＳＯの１０種の溶媒で赤紫の色を呈していたが、Ｅｔ２Ｏ、ＣＨＣｌ３の溶媒では沈殿が検出された。また、Ｃ６Ｈ１４の溶媒に加えＰｈＣＨ３では沈殿し無色であった。 FIG. 14 is a diagram showing the state of a solution of SilicaAuNR in water and an organic solvent before inversion mixing (upper stage) after 24 hours and after ultrasonic irradiation and after inversion mixing (lower stage). SilicaAuNR is 10 kinds of solvents of H 2 O, MeOH, EtOH, Et 2 O, THF, Me 2 CO, CHCl 3 , CH 2 Cl 2 , MeCN, DMSO before inversion mixing after 24 h (FIG. 14 upper stage). However, precipitation was detected with Et 2 O and CHCl 3 solvents. In addition to the solvent of C 6 H 14 , PhCH 3 precipitated and was colorless.
その後、超音波照射後さらに転倒混合する（図１４下段）とＨ２Ｏ、ＭｅＯＨ、ＥｔＯＨ、Ｅｔ２Ｏ、ＴＨＦ、Ｍｅ２ＣＯ、ＣＨＣｌ３、ＣＨ２Ｃｌ２、ＰｈＣＨ３、ＭｅＣＮ、ＤＭＳＯの各溶媒すべてで赤紫の色を呈した。またＣ６Ｈ１４の溶媒では沈殿を生じ無色であった。そのため、吸収スペクトル測定はＣ６Ｈ１４の溶媒を除く１１種の溶媒について行った。２４ｈ後における水及び有機溶媒でのＳｉｌｉｃａＡｕＮＲの吸収スペクトルの測定結果を図１５に示す。この結果は、ＳｉｌｉｃａＡｕＮＲは、０ｈ時点とほぼ同じである。図１３および図１５に示すように各スペクトルはピークを持つのでＣ６Ｈ１４を除いてＳｉｌｉｃａＡｕＮＲは分散されていることがわかる。 Then, after ultrasonic irradiation, it is further mixed by inversion (the lower part of FIG. 14), and each of H 2 O, MeOH, EtOH, Et 2 O, THF, Me 2 CO, CHCl 3 , CH 2 Cl 2 , PhCH 3 , MeCN, DMSO All the solvents exhibited a magenta color. In addition, the C 6 H 14 solvent was precipitated and was colorless. Therefore, the absorption spectrum measurement was performed for 11 types of solvents excluding the C 6 H 14 solvent. The measurement result of the absorption spectrum of SilicaAuNR in water and an organic solvent after 24 hours is shown in FIG. As a result, SilicaAuNR is almost the same as that at 0h. As shown in FIGS. 13 and 15, since each spectrum has a peak, it can be seen that SilicaAuNR is dispersed except for C 6 H 14 .
４．ＳｉｌｉｃａＡｕＮＲの再分散性
続いて、ＡｕＮＲならびにＳｉｌｉｃａＡｕＮＲの再分散性の検討を行った。
4). Redispersibility of SilicaAuNR Subsequently, redispersibility of AuNR and SilicaAuNR was examined.
４−１．ＡｕＮＲ／ｍｉｌｌｉＱとＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの再分散性 4-1. Redispersibility of AuNR / milliQ and SilicaAuNR / milliQ
まず、１．５ｍＬ容エッペンドルフチューブにＡｕＮＲ／ｍｉｌｌｉＱ、ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱを１．０ｍＬずつ用意し、それぞれ吸収スペクトル測定を行った。ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱはＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨを１．５ｍＬ容エッペンドルフチューブに１．０ｍＬ移し、遠心分離（４０００ｒｐｍ［１４４９×ｇ］、３０ｍｉｎ（分）、２５℃）し、上清を除き、同量（約１．０ｍＬ）のｍｉｌｌｉＱで再分散することで作製した。 First, 1.0 mL each of AuNR / milliQ and SilicaAuNR / milliQ were prepared in a 1.5 mL Eppendorf tube, and absorption spectra were measured for each. SilicaAuNR / milliQ was transferred 1.0 mL of SilicaAuNR / MeOH to a 1.5 mL Eppendorf tube, centrifuged (4000 rpm [1449 × g], 30 min (min), 25 ° C.), the supernatant was removed, and the same amount (about 1 (.0 mL) was redispersed with milliQ.
更に、ＡｕＮＲ／ｍｉｌｌｉＱ、ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの減圧乾燥下における再分散性を検討するために、これらを遠心分離（４０００ｒｐｍ［１４４９×ｇ］、３０ｍｉｎ（分）、２５℃）し、上清を除き、エッペンドルフチューブの蓋を開けた状態で静置し、デシケーター中で２４ｈ減圧乾燥した。２４ｈ後、同量（約８５０μＬ）のｍｉｌｌｉＱで超音波を１ｍｉｎ（分）ずつ照射し再分散し、それぞれ吸収スペクトル測定を行った。図１６にＡｕＮＲおよびＳｉｌｉｃａＡｕＮＲのｍｉｌｌｉＱ（Ｈ２Ｏ）溶液の次の４つの時点における状態を示す。図１６左上は遠心分離前、図１６右上は減圧乾燥前、図１６左下は減圧乾燥後、図１６右下は再分散後のｍｉｌｌｉＱ（Ｈ２Ｏ）溶液の状態を示している。なお、各時点それぞれについてＡｕＮＲを左、ＳｉｌｉｃａＡｕＮＲを右に示している。また、再分散前後におけるそれぞれの吸収スペクトルを図１７〜図１９に示す。図１７は乾燥させ再分散した前後のＡｕＮＲ／ｍｉｌｌｉＱの吸収スペクトルを示す図、図１８は乾燥させ再分散した前後のＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの吸収スペクトルを示す図、図１９は乾燥させ再分散した前後のＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの長軸由来のλｍａｘで規格化した吸収スペクトル（すなわちＳｉｌｉｃａＡｕＮＲの長軸に起因する吸収光の波長の最大値（λｍａｘ）で規格化した吸収スペクトル）を示す図である。したがって図１９の縦軸は規格値であり任意単位(ａ．ｕ．）である。なお、測定は、光路長１ｃｍのガラスセルを使用し、ｍｉｌｌｉＱで１０倍希釈したものを測定した。また、再分散した後のＡｕＮＲ／ｍｉｌｌｉＱ(図２０）、ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの沈殿（図２１）、ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの上清(図２２）をＳＥＭ観察した。図１７〜図１９で明らかなようにＡｕＮＲとＳｉｌｉｃａＡｕＮＲとはほぼ同じ波長で吸光度のピークを備え、ＳｉｌｉｃａＡｕＮＲはｍｉｌｌｉＱの再分散前後で長軸に起因するλｍａｘで規格化した吸収スペクトルが同様の傾向を示している。これまで示したように、金ナノロッドには吸収スペクトルに特有のピークを備えている。このピークは、ＡｕＮＲの異方性形状に由来している。各吸収スペクトルを比較すると、図１７のＡｕＮＲよりも図１８のＳｉｌｉｃａＡｕＮＲの方がピークの強度が高いことから再分散出来ている事が確認できる。ここでＳｉｌｉｃａＡｕＮＲの再分散前後で比較すると、強度は変化している。しかしながら図１９に示すようにλｍａｘで規格化した吸収スペクトルでは、そのスペクトルの形状はほぼ同じであり、再分散されていることが確認できた。 Further, in order to examine the redispersibility of AuNR / milliQ and SilicaAuNR / milliQ under reduced pressure drying, these were centrifuged (4000 rpm [1449 × g], 30 min (min), 25 ° C.), and the supernatant was removed. The Eppendorf tube was left open with the lid open and dried under reduced pressure in a desiccator for 24 hours. After 24 hours, ultrasonic waves were irradiated for 1 min (minutes) with the same amount (about 850 μL) of milliQ for redispersion, and absorption spectra were measured respectively. FIG. 16 shows states of AuNR and SilicaAuNR in the following four time points of the milliQ (H 2 O) solution. The upper left of FIG. 16 shows the state of the milliQ (H 2 O) solution before centrifugation, the upper right of FIG. 16 shows the state before drying under reduced pressure, the lower left of FIG. For each time point, AuNR is shown on the left and SilicaAuNR is shown on the right. Moreover, each absorption spectrum before and behind re-dispersion is shown in FIGS. FIG. 17 is a diagram showing absorption spectra of AuNR / milliQ before and after being dried and redispersed, FIG. 18 is a diagram showing absorption spectra of SilicaAuNR / milliQ before and after being dried and redispersed, and FIG. 19 is a diagram before and after being dried and redispersed. It is a figure which shows the absorption spectrum normalized by (lambda) max derived from the long axis of SilicaAuNR / milliQ (namely, the absorption spectrum normalized by the maximum value (λmax) of the wavelength of the absorbed light resulting from the long axis of SilicaAuNR). Accordingly, the vertical axis in FIG. 19 is a standard value and is an arbitrary unit (au). The measurement was performed using a glass cell having an optical path length of 1 cm and diluted 10 times with milliQ. Further, the AuNR / milliQ after redispersion (FIG. 20), the precipitation of SilicaAuNR / milliQ (FIG. 21), and the supernatant of SilicaAuNR / milliQ (FIG. 22) were observed by SEM. As is apparent from FIGS. 17 to 19, AuNR and SilicaAuNR have absorbance peaks at almost the same wavelength, and SilicaAuNR has a similar tendency in absorption spectra normalized by λmax due to the long axis before and after redispersion of milliQ. Show. As shown so far, gold nanorods have a characteristic peak in the absorption spectrum. This peak is derived from the anisotropic shape of AuNR. Comparing the respective absorption spectra, it can be confirmed that redistribution is possible because SilicaAuNR in FIG. 18 has higher peak intensity than AuNR in FIG. Here, when comparing before and after redispersion of SilicaAuNR, the intensity changes. However, as shown in FIG. 19, in the absorption spectrum normalized by λmax, the shape of the spectrum is almost the same, and it was confirmed that the spectrum was redispersed.
４−２．ＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの再分散性 4-2. SilicaAuNR / MeOH redispersibility
まず、１．５ｍＬ容エッペンドルフチューブにＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨを１．０ｍＬ用意し、吸収スペクトル測定を行った。 First, 1.0 mL of SilicaAuNR / MeOH was prepared in a 1.5 mL Eppendorf tube, and the absorption spectrum was measured.
更に、ＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの減圧乾燥下における再分散性を検討するために、これらを遠心分離（４０００ｒｐｍ［１４４９×ｇ］、３０ｍｉｎ（分）、２５℃）し、上清を除き、エッペンドルフチューブの蓋を開けた状態で静置し、デシケーター中で２４ｈ減圧乾燥した。２４ｈ後、同量（約８５０μＬ）のＭｅＯＨで超音波を１ｍｉｎ（分）ずつ照射し再分散し、吸収スペクトル測定を行った。図２３にＳｉｌｉｃａＡｕＮＲのＭｅＯＨ溶液の状態を示す。ここで図２３左上は遠心分離前、図２３右上は減圧乾燥前、図２３左下は減圧乾燥後、図２３右下は再分散後のそれぞれのＭｅＯＨ溶液の状態を示している。また、再分散前後における吸収スペクトルの測定結果を図２４〜図２５に示す。図２４は乾燥させ再分散した前後のＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの吸収スペクトルを示す図、図２５は乾燥させ再分散した前後のＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの長軸由来のλｍａｘで規格化した吸収スペクトル（すなわちＳｉｌｉｃａＡｕＮＲの長軸に起因する吸収光の波長の最大値（λｍａｘ）で規格化した吸収スペクトル）を示す図である。したがって図２５の縦軸は規格値であり任意単位(ａ．ｕ．）である。なお、測定は、光路長１ｃｍのガラスセルを使用し、ＭｅＯＨで１０倍希釈したものを測定した。また、再分散した後のＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨをＳＥＭ観察した（図２６）。 Furthermore, in order to examine the redispersibility of SilicaAuNR / MeOH under reduced pressure drying, these were centrifuged (4000 rpm [1449 × g], 30 min (min), 25 ° C.), the supernatant was removed, and the Eppendorf tube lid was removed. Was left open and dried under reduced pressure in a desiccator for 24 hours. After 24 hours, the same amount (approximately 850 μL) of MeOH was irradiated for 1 minute (minute) with ultrasonic waves to redisperse, and the absorption spectrum was measured. FIG. 23 shows the state of SilicaAuNR in MeOH. Here, the upper left of FIG. 23 shows the state of each MeOH solution before centrifugation, the upper right of FIG. 23 shows the state of MeOH before drying under reduced pressure, the lower left of FIG. 23 shows after drying under reduced pressure, and the lower right of FIG. Moreover, the measurement result of the absorption spectrum before and behind redispersion is shown in FIGS. FIG. 24 is a diagram showing absorption spectra of SilicaAuNR / MeOH before and after being dried and redispersed. FIG. 25 is an absorption spectrum normalized by λmax derived from the major axis of SilicaAuNR / MeOH before and after being dried and redispersed (that is, the length of SilicaAuNR). It is a figure which shows the absorption spectrum normalized with the maximum value ((lambda) max) of the wavelength of the absorbed light resulting from an axis | shaft. Therefore, the vertical axis in FIG. 25 is a standard value and is an arbitrary unit (au). The measurement was performed using a glass cell having an optical path length of 1 cm and diluted 10 times with MeOH. Further, SilicaAuNR / MeOH after redispersion was observed by SEM (FIG. 26).
４−３．ＡｕＮＲ／ＤＭＳＯとＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯの再分散性
まず、ＡｕＮＲ／ｍｉｌｌｉＱとＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨを１．５ｍＬ容エッペンドルフチューブに１．０ｍＬ移し、遠心分離（４０００ｒｐｍ［１４４９×ｇ］、３０ｍｉｎ（分）、２５℃）し、上清を除き、同量（約１．０ｍＬ）のＤＭＳＯで再分散する。このようにしてＡｕＮＲ／ＤＭＳＯとＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯを作製し、それぞれ吸収スペクトル測定を行った。
4-3. Redispersibility of AuNR / DMSO and SilicaAuNR / DMSO First, 1.0 mL of AuNR / milliQ and SilicaAuNR / MeOH was transferred to a 1.5 mL Eppendorf tube and centrifuged (4000 rpm [1449 × g], 30 min (min), 25 ° C. Remove the supernatant and redisperse with the same volume (approximately 1.0 mL) of DMSO. In this manner, AuNR / DMSO and SilicaAuNR / DMSO were prepared, and absorption spectra were measured respectively.
更に、遠心分離（４０００ｒｐｍ［１４４９×ｇ］、３０ｍｉｎ（分）、２５℃）し、上清を除き、エッペンドルフチューブの蓋を開けた状態で静置し、デシケーター中でダイヤフラムポンプを使用して４２ｈ減圧乾燥した。しかし、これでは乾燥が不十分だった為、オイルポンプを使用して更に６ｈ減圧乾燥した。６ｈ後、同量（約８５０μＬ）のＤＭＳＯで超音波を１ｍｉｎ（分）ずつ照射し再分散し、それぞれ吸収スペクトル測定を行った。図２７にＡｕＮＲおよびＳｉｌｉｃａＡｕＮＲのＤＭＳＯ溶液の次の６つの時点における状態を示す。図２７左上は遠心分離前、図２７中上は減圧乾燥前、図２７右上はダイヤフラムポンプ減圧乾燥後、図２７左下はオイルポンプ減圧乾燥後、図２７中下は再分散後、図２７右下は超音波照射後のそれぞれのＤＭＳＯ溶液の状態を示している。なお、各時点それぞれについてＡｕＮＲを左、ＳｉｌｉｃａＡｕＮＲを右に示している。また、再分散前後におけるそれぞれの吸収スペクトルを図２８〜図３０に示す。図２８は乾燥させ再分散した前後のＡｕＮＲ／ＤＭＳＯの吸収スペクトルを示す図、図２９は乾燥させ再分散した前後のＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯの吸収スペクトルを示す図、図３０は乾燥させ再分散した前後のＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯの長軸由来のλｍａｘで規格化した吸収スペクトル（すなわちＳｉｌｉｃａＡｕＮＲの長軸に起因する吸収光の波長の最大値（λｍａｘ）で規格化した吸収スペクトル）を示す図である。したがって図３０の縦軸は規格値であり任意単位(ａ．ｕ．）である。なお、測定は、光路長１ｃｍのガラスセルを使用し、ＤＭＳＯで１０倍希釈したものを測定した。再分散した後のＡｕＮＲ／ｍｉｌｌｉＱの沈殿（図３１）、ＡｕＮＲ／ｍｉｌｌｉＱの上清(図３２）、ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの沈殿（図３３）、ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの上清(図３４）をＳＥＭ観察した。 Further, the mixture is centrifuged (4000 rpm [1449 × g], 30 min (min), 25 ° C.), the supernatant is removed, the Eppendorf tube is left open, and left to stand for 42 h using a diaphragm pump in a desiccator. It was dried under reduced pressure. However, since this was insufficient drying, it was further dried under reduced pressure for 6 hours using an oil pump. After 6 hours, ultrasonic waves were irradiated for 1 min (minutes) with the same amount (about 850 μL) of DMSO for redispersion, and absorption spectra were measured respectively. FIG. 27 shows the states of the following six time points of the DMSO solution of AuNR and SilicaAuNR. The upper left of FIG. 27 is before centrifugation, the upper part of FIG. 27 is before drying under reduced pressure, the upper right part of FIG. 27 is after drying under reduced pressure of the diaphragm pump, the lower left part of FIG. 27 is after drying under reduced pressure of the oil pump, the lower part of FIG. Indicates the state of each DMSO solution after ultrasonic irradiation. For each time point, AuNR is shown on the left and SilicaAuNR is shown on the right. Moreover, each absorption spectrum before and behind re-dispersion is shown in FIGS. FIG. 28 shows absorption spectra of AuNR / DMSO before and after drying and redispersion, FIG. 29 shows absorption spectra of SilicaAuNR / DMSO before and after drying and redispersion, and FIG. 30 shows before and after drying and redispersion. It is a figure which shows the absorption spectrum normalized by (lambda) max derived from the long axis of SilicaAuNR / DMSO (namely, the absorption spectrum normalized by the maximum value (λmax) of the wavelength of the absorbed light resulting from the long axis of SilicaAuNR). Therefore, the vertical axis in FIG. 30 is a standard value and is an arbitrary unit (au). The measurement was performed using a glass cell having an optical path length of 1 cm and diluted 10 times with DMSO. After redispersion, precipitation of AuNR / milliQ (FIG. 31), supernatant of AuNR / milliQ (FIG. 32), precipitation of SilicaAuNR / milliQ (FIG. 33), and supernatant of SilicaAuNR / milliQ (FIG. 34) were observed by SEM. .
５．ＳｉｌｉｃａＡｕＮＲの熱耐性 5. Thermal resistance of SilicaAuNR
続いて、経時変化におけるＡｕＮＲとＳｉｌｉｃａＡｕＮＲの熱耐性の検討を行った。 Subsequently, the heat resistance of AuNR and SilicaAuNR over time was examined.
５−１．ＡｕＮＲ／ｍｉｌｌｉＱとＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの熱耐性 5-1. Thermal resistance of AuNR / milliQ and SilicaAuNR / milliQ
まず、１４ｍＬ容ガラス製スナップバイアル瓶にＡｕＮＲ／ｍｉｌｌｉＱ、ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱを５．０ｍＬずつ用意し、それぞれ吸収スペクトル測定を行った。吸収スペクトルの測定後、６０℃に設定した恒温水槽中に保存し、経過時間毎にそれぞれ吸収スペクトル測定を行った。最初（０ｈ）を含め、０．５ｈ後、１．０ｈ後、２．０ｈ後、３．０ｈ後、６．０ｈ後、１２ｈ後、１８ｈ後、２４ｈ後に計９回測定を行った。なお、測定は、光路長１ｃｍのガラスセルを使用し、ｍｉｌｌｉＱで１０倍希釈したものを測定した。これら吸収スペクトルの測定結果を図３５〜図３８に示す。図３５は経時変化（０ｈ〜２４ｈ）におけるＡｕＮＲ／ｍｉｌｌｉＱの吸収スペクトル、図３６は長軸由来のλｍａｘで規格化した経時変化（０ｈ〜２４ｈ）におけるＡｕＮＲ／ｍｉｌｌｉＱの吸収スペクトル、図３７は経時変化（０ｈ〜２４ｈ）におけるＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの吸収スペクトル、図３８は長軸由来のλｍａｘで規格化した経時変化（０ｈ〜２４ｈ）におけるＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの吸収スペクトルをそれぞれ示す。したがって図３６、図３８の縦軸は規格値であり任意単位(ａ．ｕ．）である。 First, 5.0 mL each of AuNR / milliQ and SilicaAuNR / milliQ were prepared in a 14 mL glass snap vial, and absorption spectra were measured for each. After the measurement of the absorption spectrum, it was stored in a constant temperature water bath set at 60 ° C., and the absorption spectrum was measured for each elapsed time. Including the first (0 h), measurements were performed 9 times in total after 0.5 h, 1.0 h, 2.0 h, 3.0 h, 6.0 h, 12 h, 18 h, and 24 h. The measurement was performed using a glass cell having an optical path length of 1 cm and diluted 10 times with milliQ. The measurement results of these absorption spectra are shown in FIGS. 35 shows the absorption spectrum of AuNR / milliQ over time (0h to 24h), FIG. 36 shows the absorption spectrum of AuNR / milliQ over time (0h to 24h) normalized by λmax derived from the long axis, and FIG. 37 shows the change over time. The absorption spectrum of SilicaAuNR / milliQ at (0h-24h) and FIG. 38 show the absorption spectrum of SilicaAuNR / milliQ at time-dependent changes (0h-24h) normalized by λmax derived from the long axis. Therefore, the vertical axis in FIGS. 36 and 38 is a standard value and is an arbitrary unit (au).
５−２．ＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの熱耐性
次に、１４ｍＬ容ガラス製スナップバイアル瓶にＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨを５．０ｍＬ用意し、吸収スペクトル測定を行った。吸収スペクトルの測定後、６０℃に設定した恒温水槽中に保存し、経過時間毎にそれぞれ吸収スペクトル測定を行った。最初（０ｈ）を含め、０．５ｈ後、１．０ｈ後、２．０ｈ後、３．０ｈ後、６．０ｈ後、１２ｈ後、１８ｈ後、２４ｈ後に計９回測定を行った。なお、測定は、光路長１ｃｍのガラスセルを使用し、ＭｅＯＨで１０倍希釈したものを測定した。これら吸収スペクトルの測定結果を図３９〜図４０に示す。図３９は経時変化（０ｈ〜２４ｈ）におけるＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの吸収スペクトル、図４０は長軸由来のλｍａｘで規格化した経時変化（０ｈ〜２４ｈ）におけるＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの吸収スペクトルである。したがって図４０の縦軸は規格値であり任意単位(ａ．ｕ．）である。
5-2. Thermal Resistance of SilicaAuNR / MeOH Next, 5.0 mL of SilicaAuNR / MeOH was prepared in a 14 mL glass snap vial and the absorption spectrum was measured. After the measurement of the absorption spectrum, it was stored in a constant temperature water bath set at 60 ° C., and the absorption spectrum was measured for each elapsed time. Including the first (0 h), measurements were performed 9 times in total after 0.5 h, 1.0 h, 2.0 h, 3.0 h, 6.0 h, 12 h, 18 h, and 24 h. The measurement was performed using a glass cell having an optical path length of 1 cm and diluted 10 times with MeOH. The measurement results of these absorption spectra are shown in FIGS. 39 shows the absorption spectrum of SilicaAuNR / MeOH over time (0h-24h), and FIG. 40 shows the absorption spectrum of SilicaAuNR / MeOH over time (0h-24h) normalized by λmax derived from the long axis. Therefore, the vertical axis in FIG. 40 is a standard value and is an arbitrary unit (au).
５−３．ＡｕＮＲ／ＤＭＳＯとＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯの熱耐性
さらに、ＡｕＮＲ／ｍｉｌｌｉＱとＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨを１５ｍＬ容プラスチック製遠心管に５．０ｍＬ移し、遠心分離（４０００ｒｐｍ［１５０２×ｇ］、３０ｍｉｎ（分）、２５℃）し、上清を除き、同量（約５．０ｍＬ）のＤＭＳＯで再分散をした。このようにしてＡｕＮＲ／ＤＭＳＯとＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯを作製した。１４ｍＬ容ガラス製スナップバイアル瓶にＡｕＮＲ／ＤＭＳＯとＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯをそれぞれ５．０ｍＬ移し替え、それぞれ吸収スペクトル測定を行った。吸収スペクトルの測定後、６０℃に設定した恒温水槽中に保存し、経過時間毎にそれぞれ吸収スペクトル測定を行った。最初（０ｈ）を含め、０．５ｈ後、１．０ｈ後、２．０ｈ後、３．０ｈ後、６．０ｈ後、１２ｈ後、１８ｈ後、２４ｈ後に計９回測定を行った。なお、測定は、光路長１ｃｍのガラスセルを使用し、ＡｕＮＲ／ｍｉｌｌｉＱ、ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱはｍｉｌｌｉＱ、ＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨはＭｅＯＨで１０倍希釈したものを測定した。これら吸収スペクトルの測定結果を図４１〜図４４に示す。図４１は経時変化（０ｈ〜２４ｈ）におけるＡｕＮＲ／ＤＭＳＯの吸収スペクトル、図４２は長軸由来のλｍａｘで規格化した経時変化（０ｈ〜２４ｈ）におけるＡｕＮＲ／ＤＭＳＯの吸収スペクトル、図４３は経時変化（０ｈ〜２４ｈ）におけるＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯの吸収スペクトル、図４４は長軸由来のλｍａｘで規格化した経時変化（０ｈ〜２４ｈ）におけるＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯの吸収スペクトルである。したがって図４２、図４４の縦軸は規格値であり任意単位(ａ．ｕ．）である。
5-3. Heat resistance of AuNR / DMSO and SilicaAuNR / DMSO Further, 5.0 mL of AuNR / milliQ and SilicaAuNR / MeOH was transferred to a 15 mL plastic centrifuge tube and centrifuged (4000 rpm [1502 × g], 30 min (min), 25 ° C.) The supernatant was removed and redispersed with the same amount (about 5.0 mL) of DMSO. In this way, AuNR / DMSO and SilicaAuNR / DMSO were produced. 5.0 mL each of AuNR / DMSO and SilicaAuNR / DMSO was transferred to a 14 mL glass snap vial, and absorption spectra were measured. After the measurement of the absorption spectrum, it was stored in a constant temperature water bath set at 60 ° C., and the absorption spectrum was measured for each elapsed time. Including the first (0 h), measurements were performed 9 times in total after 0.5 h, 1.0 h, 2.0 h, 3.0 h, 6.0 h, 12 h, 18 h, and 24 h. The measurement was performed using a glass cell having an optical path length of 1 cm, AuNR / milliQ, SilicaAuNR / milliQ were diluted with milliQ, and SilicaAuNR / MeOH was diluted 10 times with MeOH. The measurement results of these absorption spectra are shown in FIGS. 41 shows the absorption spectrum of AuNR / DMSO over time (0h to 24h), FIG. 42 shows the absorption spectrum of AuNR / DMSO over time (0h to 24h) normalized by λmax derived from the long axis, and FIG. 43 shows the change over time. 44 shows the absorption spectrum of SilicaAuNR / DMSO at (0h-24h), and FIG. 44 shows the absorption spectrum of SilicaAuNR / DMSO at time-dependent changes (0h-24h) normalized by λmax derived from the long axis. Therefore, the vertical axis of FIG. 42 and FIG. 44 is a standard value and is an arbitrary unit (au).
６０℃に設定した恒温水槽中に２４ｈ静置した後のＡｕＮＲ／ＤＭＳＯ、ＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯをＳＥＭ観察した。図４５は２４ｈ後のＡｕＮＲ／ＤＭＳＯのＳＥＭ像、図４６は２４ｈ後のＳｉｌｉｃａＡｕＮＲ／ＤＭＳＯのＳＥＭ像である。 AuNR / DMSO and SilicaAuNR / DMSO after standing for 24 hours in a constant temperature water bath set at 60 ° C. were observed by SEM. FIG. 45 is a SEM image of AuNR / DMSO after 24 hours, and FIG. 46 is a SEM image of SilicaAuNR / DMSO after 24 hours.
６．ＳｉｌｉｃａＡｕＮＲの吸収スペクトル測定 6). Absorption spectrum measurement of SilicaAuNR
最後に、ＡｕＮＲとＳｉｌｉｃａＡｕＮＲを比較し、それぞれの異なる濃度における吸光度をプロットすることでＬａｍｂｅｒｔ−Ｂｅｅｒの法則に従うことを確認した。 Finally, AuNR and SilicaAuNR were compared, and it was confirmed that the absorbance at each different concentration was plotted to follow Lambert-Beer's law.
６−１．ＡｕＮＲ／ｍｉｌｌｉＱとＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの吸光度測定 6-1. Absorbance measurement of AuNR / milliQ and SilicaAuNR / milliQ
まずＡｕＮＲ／ｍｉｌｌｉＱの吸光度測定について説明する。ＡｕＮＲ／ｍｉｌｌｉＱを用いて以下の条件で吸収スペクトル測定を行った。表１に希釈条件（サンプルａ〜ｐ）でのＡｕＮＲ／ｍｉｌｌｉＱの金終濃度を示す。また表２に濃縮条件（サンプルｑ〜ｓ）でのＡｕＮＲ／ｍｉｌｌｉＱの金終濃度を示す。なお、測定では、光路長１ｍｍのガラスセルを使用し、仕様容器は表１、表２中のサンプルａ〜サンプルｐは１．５ｍＬ容エッペンドルフチューブを、表２中のサンプルｑ〜アンプルｓは１５ｍＬ容プラスチック製遠心管を、それぞれ使用した。吸収スペクトル測定の結果を図４７〜図４９に示す。図４７は濃度変化におけるＡｕＮＲ／ｍｉｌｌｉＱの吸収スペクトル変化、図４８は長軸由来のλｍａｘで規格化したＡｕＮＲ／ｍｉｌｌｉＱの吸収スペクトル（ただしサンプルｓは除く）、図４９は異なる濃度条件下でのＡｂｓ５２７（ここでＡｂｓ５２７は波長５２７ｎｍの吸光度であり、この波長５２７ｎｍは短軸由来のλｍａｘ）におけるＡｕＮＲ／ｍｉｌｌｉＱの吸光度のプロットである。ここで図４８の縦軸は規格値であり任意単位(ａ．ｕ．）である。 First, the absorbance measurement of AuNR / milliQ will be described. Absorption spectrum measurement was performed using AuNR / milliQ under the following conditions. Table 1 shows the gold final concentration of AuNR / milliQ under dilution conditions (samples a to p). Table 2 shows the final gold concentration of AuNR / milliQ under the concentration conditions (samples q to s). In the measurement, a glass cell having an optical path length of 1 mm is used, the specification containers are 1.5 mL Eppendorf tubes for samples a to p in Tables 1 and 2, and 15 mL for samples q to ampoules s in Table 2. Each plastic centrifuge tube was used. The results of the absorption spectrum measurement are shown in FIGS. FIG. 47 shows changes in the absorption spectrum of AuNR / milliQ with changes in concentration, FIG. 48 shows the absorption spectrum of AuNR / milliQ normalized by λmax derived from the long axis (except for sample s), and FIG. 49 shows Abs527 under different concentration conditions. Here, Abs 527 is the absorbance at a wavelength of 527 nm, and this wavelength 527 nm is a plot of the absorbance of AuNR / milliQ at λmax derived from the short axis. Here, the vertical axis of FIG. 48 is a standard value and is an arbitrary unit (au).
次に、ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの吸光度測定について説明する。ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱはＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨを１５ｍＬ容のプラスチック製遠心管に１０ｍＬずつ分け４本作製し（全量４０ｍＬ）、遠心分離（６０００ｒｐｍ［３５４２×ｇ］、３０ｍｉｎ(分）、２５℃）し、上清を除き、同量（約１０ｍＬ）のｍｉｌｌｉＱを入れ、超音波を１０ｓ（秒）照射し再分散をすることで作製した。ＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱを用いて以下の条件で吸収スペクトル測定を行った。表３は希釈条件（サンプルａ〜ｊ）でのＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの金終濃度を、表４は濃縮条件（サンプルｋ〜ｓ）でのＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの金終濃度を示す。なお、測定では、光路長１ｍｍのガラスセルを使用し、仕様容器は表３、表４中のサンプルａ〜サンプルｐでは１．５ｍＬ容エッペンドルフチューブを、表４中のサンプルｑ〜アンプルｓでは１５ｍＬ容プラスチック製遠心管を、それぞれ使用した。吸収スペクトル測定の結果を図５０〜図５３に示す。図５０は濃度変化におけるＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの吸収スペクトル変化、図５１は長軸由来のλｍａｘで規格化したＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの吸収スペクトル、図５２は異なる濃度条件下でのＡｂｓ５３０．５（ここでＡｂｓ５３０．５は波長５３０．５ｎｍの吸光度であり、この波長５３０．５ｎｍは短軸由来のλｍａｘ）におけるＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの吸光度のプロット、図５３は異なる濃度条件下での短軸由来のλｍａｘにおけるＡｕＮＲ／ｍｉｌｌｉＱとＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱの吸光度のプロットである。図５３において点線がＡｕＮＲ／ｍｉｌｌｉＱ、実線がＳｉｌｉｃａＡｕＮＲ／ｍｉｌｌｉＱをそれぞれ示している。また、図５１の縦軸は規格値であり任意単位(ａ．ｕ．）である。 Next, the absorbance measurement of SilicaAuNR / milliQ will be described. SilicaAuNR / miliQ was prepared by dividing SilicaAuNR / MeOH into 10 mL each in a 15 mL plastic centrifuge tube (total volume 40 mL), centrifuged (6000 rpm [3542 × g], 30 min (min), 25 ° C.), supernatant The same amount (about 10 mL) of milliQ was added, and ultrasonic waves were applied for 10 s (seconds) to redisperse. Absorption spectra were measured using SilicaAuNR / milliQ under the following conditions. Table 3 shows the final gold concentration of SilicaAuNR / milliQ under dilution conditions (samples a to j), and Table 4 shows the final gold concentration of SilicaAuNR / milliQ under the concentration conditions (samples k to s). In the measurement, a glass cell having an optical path length of 1 mm was used, the specification containers were 1.5 mL Eppendorf tubes for samples a to p in Tables 3 and 4, and 15 mL for samples q to ampoules s in Table 4. Each plastic centrifuge tube was used. The results of the absorption spectrum measurement are shown in FIGS. FIG. 50 shows the change in absorption spectrum of SilicaAuNR / milliQ with changes in concentration, FIG. 51 shows the absorption spectrum of SilicaAuNR / milliQ normalized by λmax derived from the long axis, and FIG. 52 shows Abs530.5 (where Abs530. 5 is absorbance at a wavelength of 530.5 nm, and the wavelength 530.5 nm is a plot of absorbance of SilicaAuNR / milliQ at λmax), FIG. 53 is AuNR / milliQ at λmax from different axes under different concentration conditions. And SilicaAuNR / milliQ absorbance plots. In FIG. 53, the dotted line indicates AuNR / milliQ, and the solid line indicates SilicaAuNR / milliQ. In addition, the vertical axis in FIG. 51 is a standard value and is an arbitrary unit (au).
６−２．ＡｕＮＲ／ＭｅＯＨとＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの吸光度測定 6-2. Absorbance measurement of AuNR / MeOH and SilicaAuNR / MeOH
まず、ＡｕＮＲ／ＭｅＯＨの吸光度測定について説明する。ＡｕＮＲ／ＭｅＯＨはＡｕＮＲ／ｍｉｌｌｉＱを１５ｍＬ容のプラスチック製遠心管に１０ｍＬずつ分け４本作製し （全量４０ｍＬ）、遠心分離（６０００ｒｐｍ［３５４２×ｇ］、３０ｍｉｎ（分）、２５℃）し、上清を除き、同量（約１０ｍＬ）のＭｅＯＨを入れ、超音波を１０ｓ（秒）照射し再分散をすることで作製した。ＡｕＮＲ／ＭｅＯＨを用いて以下の条件で吸収スペクトル測定を行った． 表５は希釈条件（サンプルａ〜ｊ）でのＡｕＮＲ／ＭｅＯＨの金終濃度、表６は濃縮条件（サンプルｋ〜ｓ）でのＡｕＮＲ／ＭｅＯＨの金終濃度を示す。なお、測定では、光路長１ｍｍのガラスセルを使用し、仕様容器は表５、表６中のサンプルａ〜サンプルｐでは１．５ｍＬ容エッペンドルフチューブを、表６中のサンプルｑ〜アンプルｓでは１５ｍＬ容プラスチック製遠心管を、それぞれ使用した。吸収スペクトル測定の結果を図５４〜図５６に示す。図５４は濃度変化におけるＡｕＮＲ／ＭｅＯＨの吸収スペクトル変化、図５５は長軸由来のλｍａｘで規格化したＡｕＮＲ／ＭｅＯＨの吸収スペクトル、図５６は異なる濃度条件下でのＡｂｓ５３２（ここでＡｂｓ５３２は波長５３２ｎｍの吸光度であり、この波長５３２ｎｍは短軸由来のλｍａｘ）におけるＡｕＮＲ／ＭｅＯＨの吸光度のプロットである。また図５５の縦軸は規格値であり任意単位(ａ．ｕ．）である。 First, the absorbance measurement of AuNR / MeOH will be described. AuNR / MeOH is prepared by dividing AuNR / milliQ into 15 mL plastic centrifuge tubes, 10 mL each (total volume 40 mL), centrifuged (6000 rpm [3542 × g], 30 min (min), 25 ° C.), and supernatant The same amount (about 10 mL) of MeOH was added, and ultrasonic waves were irradiated for 10 s (seconds) to redisperse. Absorption spectra were measured using AuNR / MeOH under the following conditions. Table 5 shows the gold final concentration of AuNR / MeOH under dilution conditions (samples a to j), and Table 6 shows the gold final concentration of AuNR / MeOH under concentration conditions (samples k to s). In the measurement, a glass cell having an optical path length of 1 mm was used, the specification containers were 1.5 mL Eppendorf tubes for samples a to p in Tables 5 and 6, and 15 mL for samples q to ampoules s in Table 6. Each plastic centrifuge tube was used. The results of the absorption spectrum measurement are shown in FIGS. 54 shows changes in the absorption spectrum of AuNR / MeOH with changes in concentration, FIG. 55 shows the absorption spectrum of AuNR / MeOH normalized by λmax derived from the long axis, and FIG. 56 shows Abs532 under different concentration conditions (where Abs532 has a wavelength of 532 nm). The wavelength of 532 nm is a plot of the absorbance of AuNR / MeOH at λmax) derived from the short axis. The vertical axis in FIG. 55 is a standard value and is an arbitrary unit (au).
次にＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの吸光度測定について説明する。ＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨを用いて以下の条件で吸収スペクトル測定を行った。表７は希釈条件（サンプルａ〜ｊ）でのＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの金終濃度、表８は濃縮条件（サンプルｋ〜ｓ）でのＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの金終濃度をそれぞれ示す。なお、測定では、光路長１ｍｍのガラスセルを使用し、仕様容器は表７、表８中のサンプルａ〜サンプルｐでは１．５ｍＬ容エッペンドルフチューブを、表８中のサンプルｑ〜アンプルｓは１５ｍＬ容プラスチック製遠心管を、それぞれ使用した。吸収スペクトル測定の結果を図５７〜図６０に示す。図５７は濃度変化におけるＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの吸収スペクトル変化、図５８は長軸由来のλｍａｘで規格化したＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの吸収スペクトル（サンプルｓは除く）、図５９は異なる濃度条件下でのＡｂｓ５１７．５（ここでＡｂｓ５１７．５は波長５１７．５ｎｍの吸光度であり、この波長５１７．５ｎｍは短軸由来のλｍａｘ）におけるＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの吸光度のプロット（サンプルｓは除く）、図６０は異なる濃度条件下での短軸由来のλｍａｘにおけるＡｕＮＲ／ＭｅＯＨとＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨの吸光度のプロット（ＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨのサンプルｓは除く）である。図６０における点線がＡｕＮＲ／ＭｅＯＨを、実線がＳｉｌｉｃａＡｕＮＲ／ＭｅＯＨをそれぞれ示す。また図５８の縦軸は規格値であり任意単位(ａ．ｕ．）である。 Next, the absorbance measurement of SilicaAuNR / MeOH will be described. Absorption spectra were measured under the following conditions using SilicaAuNR / MeOH. Table 7 shows the final gold concentration of SilicaAuNR / MeOH under dilution conditions (samples a to j), and Table 8 shows the final gold concentration of SilicaAuNR / MeOH under concentration conditions (samples k to s). In the measurement, a glass cell with an optical path length of 1 mm was used, the specification containers were 1.5 mL Eppendorf tubes for samples a to p in Tables 7 and 8, and 15 mL for samples q to ampoules s in Table 8. Each plastic centrifuge tube was used. The results of the absorption spectrum measurement are shown in FIGS. 57 shows the change in absorption spectrum of SilicaAuNR / MeOH with change in concentration, FIG. 58 shows the absorption spectrum of SilicaAuNR / MeOH normalized by λmax derived from the long axis (excluding sample s), and FIG. 59 shows Abs517. 5 (where Abs 517.5 is the absorbance at a wavelength of 517.5 nm, and this wavelength 517.5 nm is λmax derived from the short axis), the absorbance of SilicaAuNR / MeOH (excluding sample s), FIG. 60 shows different concentration conditions It is a plot of the absorbance of AuNR / MeOH and SilicaAuNR / MeOH at λmax derived from the short axis (excluding SilicaAuNR / MeOH sample s). The dotted line in FIG. 60 indicates AuNR / MeOH, and the solid line indicates SilicaAuNR / MeOH. The vertical axis in FIG. 58 is a standard value and is an arbitrary unit (au).
７．まとめ 7). Summary
非特許文献２において、シリカコーティング時のメタノール濃度は０．９％程度であり、検証実験を行ったところシリカコーティングされた金ナノロッドの形成はできなかった。 そのため、諸条件を変えて試行錯誤したところ、上述のように（例えば２−１項）シリカコーティング時にメタノール濃度を２５±５％まで高めることにより常温でシリカコーティングされた金ナノロッドの形成が確認された。メタノール濃度は概ね２５％±５％程度まで高めることによりシリカコートされた金ナノロッド（ＳｉｌｉｃａＡｕＮＲ）の形成が確認された。つまり安定したシリカコートされた金ナノロッド（ＳｉｌｉｃａＡｕＮＲ）の形成には、図１のステップ３（Ｓ３）におけるメタノール濃度が鍵であることがわかった。 In Non-Patent Document 2, the methanol concentration at the time of silica coating is about 0.9%, and when a verification experiment was conducted, formation of silica-coated gold nanorods was not possible. Therefore, when various conditions were changed and trial and error were conducted, formation of silica-coated gold nanorods at room temperature was confirmed by increasing the methanol concentration to 25 ± 5% during silica coating as described above (for example, item 2-1). It was. The formation of silica-coated gold nanorods (SilicaAuNR) was confirmed by increasing the methanol concentration to about 25% ± 5%. That is, it was found that the methanol concentration in Step 3 (S3) in FIG. 1 is the key to the formation of stable silica-coated gold nanorods (SilicaAuNR).
金ナノロッドはマーカー等に利用されるため、その基本特性として光の吸収特性が重要である。Ａｕに光を吸収させることでマーカーとしての効果を奏するため、コーティングによるその劣化は問題となるが、シリカコーティングは、水溶液に高分散化した溶液においてその吸収スペクトルが金ナノロッドとシリカコーティングされた金ナノロッドとの間で遜色がない(図５、図６）。 Since gold nanorods are used for markers and the like, light absorption characteristics are important as their basic characteristics. Since the Au coating absorbs light and has an effect as a marker, its degradation due to the coating becomes a problem. However, the silica coating has a gold nanorod and a silica-coated gold in its absorption spectrum in a highly dispersed solution. There is no inferiority between the nanorods (FIGS. 5 and 6).
また、この方法により作成されたシリカコーティングされた金ナノロッドを上述のように１２種の溶媒にて分散性を確認した。表９に分散性をまとめる。表９において○印は、溶媒中のシリカコーティングされた金ナノロッドの光吸収スペクトルのピークが水溶液と同じ部分で観測されたものであり、×は観測されなかったものである。つまり、シリカコーティングされたＡｕＮＲはメタノール、エタノール、ジエチルエーテル、テトラヒドロフラン、アセトン、クロロホルム、ジクロロメタン、トルエン、アセトニトリル、ＤＭＳＯの何れかの媒体でコロイド分散する。つまり、シリカコートされたＡｕＮＲはＡｕＮＲと遜色のない光吸収スペクトルを備えることによりマーカーとしての効果を奏するのみならず、ＡｕＮＲ以上に様々な溶媒(有機溶媒を含む）で高分散液をつくれることがわかった。 Moreover, the dispersibility of the silica-coated gold nanorods prepared by this method was confirmed using 12 kinds of solvents as described above. Table 9 summarizes the dispersibility. In Table 9, ◯ indicates that the peak of the light absorption spectrum of the silica-coated gold nanorod in the solvent was observed at the same portion as the aqueous solution, and × was not observed. That is, the silica-coated AuNR is colloidally dispersed in any medium of methanol, ethanol, diethyl ether, tetrahydrofuran, acetone, chloroform, dichloromethane, toluene, acetonitrile, and DMSO. In other words, silica-coated AuNR not only has an effect as a marker by providing a light absorption spectrum comparable to that of AuNR, but also can produce a high dispersion with various solvents (including organic solvents) more than AuNR. all right.
シリカコートされたＡｕＮＲは種々の溶媒で高分散するので、その目的に合った溶媒を利用した分散液は、抗原抗体を基盤としたアッセイ法の着色剤やバイオセンサ、更には体内分散などでの利用が考えられる。また様々な材料系研究でＡｕＮＲの取扱い容易となる。
Since the silica-coated AuNR is highly dispersed in various solvents, a dispersion using a solvent suitable for the purpose can be used as a colorant or biosensor for an assay method based on an antigen-antibody, and further dispersed in the body. Possible use. In addition, it becomes easy to handle AuNR in various materials research.
Claims (3)
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017022728A JP6923778B2 (en) | 2017-02-10 | 2017-02-10 | Method for synthesizing silica-coated highly dispersible gold nanorods and dispersion of synthesized gold nanorods |
| JP2021102517A JP2021152223A (en) | 2017-02-10 | 2021-06-21 | Highly dispersible silica-coated gold nanorods and dispersion liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2017022728A JP6923778B2 (en) | 2017-02-10 | 2017-02-10 | Method for synthesizing silica-coated highly dispersible gold nanorods and dispersion of synthesized gold nanorods |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021102517A Division JP2021152223A (en) | 2017-02-10 | 2021-06-21 | Highly dispersible silica-coated gold nanorods and dispersion liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2018127699A true JP2018127699A (en) | 2018-08-16 |
| JP6923778B2 JP6923778B2 (en) | 2021-08-25 |
Family
ID=63173668
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2017022728A Active JP6923778B2 (en) | 2017-02-10 | 2017-02-10 | Method for synthesizing silica-coated highly dispersible gold nanorods and dispersion of synthesized gold nanorods |
| JP2021102517A Pending JP2021152223A (en) | 2017-02-10 | 2021-06-21 | Highly dispersible silica-coated gold nanorods and dispersion liquid |
Family Applications After (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2021102517A Pending JP2021152223A (en) | 2017-02-10 | 2021-06-21 | Highly dispersible silica-coated gold nanorods and dispersion liquid |
Country Status (1)
| Country | Link |
|---|---|
| JP (2) | JP6923778B2 (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021152223A (en) * | 2017-02-10 | 2021-09-30 | 国立大学法人山梨大学 | Highly dispersible silica-coated gold nanorods and dispersion liquid |
| CN114309592A (en) * | 2021-12-30 | 2022-04-12 | 杭州电子科技大学 | Method for coating silicon dioxide on two ends of gold nanorod |
| CN114799190A (en) * | 2022-06-20 | 2022-07-29 | 杭州电子科技大学富阳电子信息研究院有限公司 | Gold nanorod film and synthesis method thereof |
| CN114918425A (en) * | 2022-06-20 | 2022-08-19 | 杭州电子科技大学富阳电子信息研究院有限公司 | Gold nanorod with broadband adjustable absorption characteristic and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010053385A (en) * | 2008-08-27 | 2010-03-11 | Ricoh Co Ltd | Silica-coated gold nanorod and method for producing the same |
| JP2015507078A (en) * | 2011-11-15 | 2015-03-05 | メタロー テクノロジーズ インターナショナル エスエー | Metal / silica core / shell nanoparticles, production method, and immunochromatographic test device including the particles |
| CN105036070A (en) * | 2015-06-30 | 2015-11-11 | 国家纳米科学中心 | Gold nanorod-silicon dioxide core-shell structure nanometer material, preparation method and application |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP6923778B2 (en) * | 2017-02-10 | 2021-08-25 | 国立大学法人山梨大学 | Method for synthesizing silica-coated highly dispersible gold nanorods and dispersion of synthesized gold nanorods |
-
2017
- 2017-02-10 JP JP2017022728A patent/JP6923778B2/en active Active
-
2021
- 2021-06-21 JP JP2021102517A patent/JP2021152223A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2010053385A (en) * | 2008-08-27 | 2010-03-11 | Ricoh Co Ltd | Silica-coated gold nanorod and method for producing the same |
| JP2015507078A (en) * | 2011-11-15 | 2015-03-05 | メタロー テクノロジーズ インターナショナル エスエー | Metal / silica core / shell nanoparticles, production method, and immunochromatographic test device including the particles |
| CN105036070A (en) * | 2015-06-30 | 2015-11-11 | 国家纳米科学中心 | Gold nanorod-silicon dioxide core-shell structure nanometer material, preparation method and application |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2021152223A (en) * | 2017-02-10 | 2021-09-30 | 国立大学法人山梨大学 | Highly dispersible silica-coated gold nanorods and dispersion liquid |
| CN114309592A (en) * | 2021-12-30 | 2022-04-12 | 杭州电子科技大学 | Method for coating silicon dioxide on two ends of gold nanorod |
| CN114799190A (en) * | 2022-06-20 | 2022-07-29 | 杭州电子科技大学富阳电子信息研究院有限公司 | Gold nanorod film and synthesis method thereof |
| CN114918425A (en) * | 2022-06-20 | 2022-08-19 | 杭州电子科技大学富阳电子信息研究院有限公司 | Gold nanorod with broadband adjustable absorption characteristic and preparation method thereof |
| CN114799190B (en) * | 2022-06-20 | 2023-04-28 | 杭州电子科技大学富阳电子信息研究院有限公司 | Gold nanorod film and synthesis method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6923778B2 (en) | 2021-08-25 |
| JP2021152223A (en) | 2021-09-30 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Micó‐Vicent et al. | Stabilized dye–pigment formulations with platy and tubular nanoclays | |
| McVey et al. | Solution synthesis, optical properties, and bioimaging applications of silicon nanocrystals | |
| JP2021152223A (en) | Highly dispersible silica-coated gold nanorods and dispersion liquid | |
| Bonacchi et al. | Luminescent chemosensors based on silica nanoparticles | |
| Li et al. | Shape-dependent surface-enhanced Raman scattering in gold–Raman-probe–silica sandwiched nanoparticles for biocompatible applications | |
| Mir et al. | Hot injection versus room temperature synthesis of CdSe quantum dots: a differential spectroscopic and bioanalyte sensing efficacy evaluation | |
| Yang et al. | Nitrogen and sulfur codoped graphene quantum dots as a new fluorescent probe for Au 3+ ions in aqueous media | |
| Konował et al. | Functionalization of organically modified silica with gold nanoparticles in the presence of lignosulfonate | |
| Sung et al. | Highly sensitive and selective fluorescence probe for Cr3+ ion detection using water-soluble CdSe QDs | |
| Achadu et al. | The interaction between graphene quantum dots grafted with polyethyleneimine and Au@ Ag nanoparticles: Application as a fluorescence “turn-on” nanoprobe | |
| US9549996B2 (en) | Matrix incorporated fluorescent porous and non-porous silica particles for medical imaging | |
| Vera et al. | Fluorescent silica nanoparticles with chemically reactive surface: Controlling spatial distribution in one-step synthesis | |
| He et al. | Fabrication of SERS-active conjugated copolymers/gold nanoparticles composite films by interface-directed assembly | |
| Ermakova et al. | The supramolecular approach to the phase transfer of carboxylic calixresorcinarene-capped silver nanoparticles | |
| Si et al. | In Situ Synthesis of Gold and Silver Nanoparticles by Using Redox‐Active Amphiphiles and Their Phase Transfer to Organic Solvents | |
| Arndt et al. | Surface functionalization of iron oxide nanoparticles and their stability in different media | |
| Blanco-Formoso et al. | Boosting the analytical properties of gold nanostars by single particle confinement into yolk porous silica shells | |
| Mishra et al. | Fabrication of gold nanoparticles on biotin-di-tryptophan scaffold for plausible biomedical applications | |
| Andrade et al. | Easy preparation of gold nanostructures supported on a thiolated silica-gel for catalysis and latent fingerprint detection | |
| Wolska-Pietkiewicz et al. | ZnO nanocrystals derived from organometallic approach: Delineating the role of organic ligand shell on physicochemical properties and nano-specific toxicity | |
| An et al. | One-step synthesis of fluorescence-enhanced carbon dots for Fe (III) on− off− on sensing, bioimaging and light-emitting devices | |
| Fahimi-Kashani et al. | Plasmonic noble metal (Ag and Au) nanoparticles: From basics to colorimetric sensing applications | |
| Zhang et al. | Multiple hybridized resonances of IR-806 chromonic molecules strongly coupled to Au nanorods | |
| Qin et al. | Polyhedral oligomeric silsesquioxane-coated nanodiamonds for multifunctional applications | |
| Yao et al. | Synthesis of pH-responsive nanocomposites of gold nanoparticles and graphene oxide and their applications in SERS and catalysis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A80 | Written request to apply exceptions to lack of novelty of invention |
Free format text: JAPANESE INTERMEDIATE CODE: A80 Effective date: 20170310 |
|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20200130 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20201014 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20201110 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210107 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20210302 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20210421 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20210525 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20210623 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6923778 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |