JP7190818B2 - 原子量子クラスター、その製造方法およびその使用方法 - Google Patents
原子量子クラスター、その製造方法およびその使用方法 Download PDFInfo
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- JP7190818B2 JP7190818B2 JP2018045461A JP2018045461A JP7190818B2 JP 7190818 B2 JP7190818 B2 JP 7190818B2 JP 2018045461 A JP2018045461 A JP 2018045461A JP 2018045461 A JP2018045461 A JP 2018045461A JP 7190818 B2 JP7190818 B2 JP 7190818B2
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Description
a.還元を遅くするための速度支配をすること、および
b.反応媒体中に低濃度の反応剤を維持すること
からなる。
Au AQCsの合成
Au AQCsの合成は、電気化学電池中で、電流電位差計を使用し、以下の実験条件の下で、1000秒間に0mA/cm2 の一定の電流密度を印加して行われる。
-作動電極:Pt(2.5cm2 )
-対向電極:Au(AQCsがそれから形成される金属)
-参照電極:Ag/AGCl
-電界溶液および安定化剤:アセトニトリル中の0.1Mのテトラブチルアンモニウム臭化物
-温度:25°C
-窒素雰囲気中に挿入
において実施された。
Ag AQCsの合成
Ag AQCsの合成は、水/AOT/イソオクタン(AOT=エアゾールOT=ナトリウムビス2エチルへキシルスルホサクシネート)のミクロエマルジョンを使用して、以下の実験条件、
-wo比=[H2O]/[AOT]=6
-イソオクタン中のAOT溶液:0.1mol/l
-AgNO3 の水溶液:0.1mol/l
-NaH2PO2・H2Oの水溶液:1mol/l
-温度:25°C
において実施された。
酸素還元における金属クラスターの電気触媒活性
金属クラスターの電気触媒活性は酸素還元における電圧電流(ボルタンメトリー)応答を比較して確認された。
e-
Mclus +O2 ⇔ Mclus--(O----O)ad ⇔ Mclus +反応生成物
過酸化水素、H2 O2 還元における金属クラスターの電気触媒活性
H2 O2 還元におけるAgクラスターの電気触媒作用は還元を受け易い単なる種類としてH2 O2 を含有するO2 の自由溶液中で測定を行なって確認された。図13は0.024MのH2 O2 および0.5MのClO4 Hを含有する水溶液における直線掃引電界電量計法を示している。測定に関して、ガラス質炭素(曲線a)および、銀クラスター、Agn(n=3,4)(曲線b)により変性されたガラス質炭素が作動電極として使用された。電位はAg/ClAg電極(飽和された)に関する。前記図において、-0.15V後、H2 O2 還元電流の増加が曲線a(クラスターの不存在)に関連して曲線b(Agクラスターの存在)において観察され;拡大において、前記増加がE=-0.45Vに関しておよそ7%であることが観察され得る。
アルコール酸化における金属クラスターの電気触媒活性
金属クラスターの電気触媒活性はアルコール酸化、かつとくにメタノール酸化における
Agクラスターの使用において観察された。前記酸化は0Vないし+1Vの範囲において発生された。前記作用をチェックするために、アセトニトリル中に分散されたAgクラスターが多結晶Pt上に堆積された。電解媒体中の安定性、すなわち、このように堆積されたクラスターのレドックスピーク(E=+1.2Vまで)の不存在をチェック後、変性された電極は0.1MNaOHを含有する1Mメタノールの水溶液に転換された。結果は図14において観察されることができ、そのさい3つの酸化ピーク(A,B,C)が異なるサイズのクラスターでのメタノールの酸化に対応するアノード掃引において観察された。Pt(変性されたPt)上に堆積されたクラスターの存在による酸化電流の最終の増加が同様に観察された。
MTTによる毒性試験
乳ガンのMCF7線の培養についてのAuおよびAgクラスターの毒性が評価され、この評価はメチル-チアゾル-テトラゾリウム(MTT)塩による細胞生存能力研究によって実施された。
6a) 図15は第1のサンプル(実施例1)に従って電気化学的に調製されかつ水(それぞれ2-5原子および6-15原子のクラスターに対応する第1のサンプルNP0.1およびNP0.2)中に分散されたAgクラスターの溶液を添加するときの結果を示している。1μMを超える濃度に関するクラスターの細胞分裂抑制作用は明瞭に観察された。これらの作用はピュロマイシンのように常習的に使用される細胞分裂抑制に匹敵する。さらに、細胞分裂抑制作用はこの場合に初期細胞の数(初期吸光度の減少)に起因して理解され得るように、一定の毒性が観察されるけれども、サンプルNP0.2がより有効であるように、クラスターの型に応じて異なることが観察される。
Claims (15)
- 2個よりも多く27個よりも少ない金属原子から構成された、安定した原子量子クラスター(AQCs)であって、その金属がAgであって、
(i)Ag原子量子クラスターを得るために1つのAg金属塩を還元し、
該還元が、
a.次亜リン酸ナトリウムを還元反応手段として用いて反応速度定数を小さな値に維持する速度支配をして、還元速度を遅くすること、および
b.‐水に溶解したAg金属塩と、
‐有機化合物に溶解した還元反応手段と
‐洗浄剤
を含む2相系において行われること、
(ii) 外部からの安定剤なしにAg原子量子クラスターを得るために、温度を減少するか、又はクラスターとの融和性がない溶媒を添加するか、或いはそれらの両方、による沈殿作用によって、前記ステップ(i)の2相系からAg原子量子クラスターを分離すること
によって得られるものであり、
該原子量子クラスターが、外部からの安定剤なしに少なくとも1時間の間、上記(i)、(ii)によってAg原子量子クラスターが沈殿している溶液中で前記金属原子の数を維持することを特徴とする、原子量子クラスター(AQCs)。 - 2個と5個との間の個数のAg原子(Agn,2<n<5)から成ることを特徴とする請求項1に記載のAQCs。
- 水に溶解された前記金属塩が硝酸銀であるか、若しくは、
前記還元反応手段が、環状、直線または分岐の飽和または不飽和炭化水素、ならびにベンゼンまたはトルエンから成るグループから選ばれる有機化合物に溶解されるか、若しくは、
洗浄剤が、スルホカルボキシル酸、アルキルアンモニウムアセテートまたは臭化物及びポリオキシエチレン誘導体から選択されるか、又は
それらのいずれか2つ又は全てを特徴とする、請求項1又は2に記載のAQCs。 - 水に溶解された前記金属塩が0.1mol/lの硝酸銀であるか、若しくは、
前記還元反応手段が、イソオクタン中に溶解されているか、若しくは、
前記洗浄剤が、ナトリウムビス2エチルへキシルスルホサクシネートを含んでいるか、若しくは、
前記(ii)の分離が沈殿によって行われるか、又は
それらのいずれか2つ、いずれか3つ若しくは全てを特徴とする、請求項1又は2に記載のAQCs。 - 1つの金属塩を還元することによって、請求項1乃至4のいずれかに記載の安定した原子量子クラスター(AQCs)を製造する方法において、該方法が、
(i)Ag原子量子クラスターを得るために1つのAg金属塩を還元し、
該還元が、
a.次亜リン酸ナトリウムを還元反応手段として用いて反応速度定数を小さな値に維持する速度支配をして、還元速度を遅くすること、および
b.‐水に溶解したAg金属塩と、
‐有機化合物に溶解した還元反応手段と
‐洗浄剤
を含む2相系において行われること、を特徴とし、
(ii) 外部からの安定剤なしにAg原子量子クラスターを得るために、温度を減少するか、又はクラスターと混ざり合わない溶媒を添加するか、或いはそれらの両方によって生じる沈殿作用によって、前記ステップ(i)の2相系からAg原子量子クラスターを分離すること
によって得られること
を含むことを特徴とする原子量子クラスター(AQCs)の製造方法。 - 水に溶解された金属塩が硝酸銀であることを特徴とする、請求項5に記載の方法。
- 還元反応手段が、環状、直線または分岐の飽和または不飽和炭化水素、ベンゼン又はトルエンの中から選択される有機化合物に溶解されていることを特徴とする、請求項5又は6に記載の方法。
- 前記有機化合物がイソオクタンであることを特徴とする、請求項7に記載の方法。
- 洗浄剤が、スルホカルボキシル酸、アルキルアンモニウムアセテートまたは臭化物及びポリオキシエチレン誘導体から選択されることを特徴とする、請求項5乃至8のいずれか1項に記載の方法。
- 前記洗浄剤が、ナトリウムビス2エチルへキシルスルホサクシネートを含んでいることを特徴とする、請求項5乃至8のいずれかに記載の方法。
- 前記(ii)の分離が沈殿によって行われることを特徴とする、請求項5乃至10のいずれか1項に記載の方法。
- 請求項1乃至4に記載のクラスター(AQCs)を蛍光センサ、バイオセンサ、磁気センサ、酸化還元剤、又は電気触媒として使用するクラスターの使用方法。
- AQCsが、還元反応において、好ましくは酸素又は過酸化水素の還元反応において、又は酸化反応において触媒として作用することを特徴とする請求項12に記載のクラスター(AQCs)の使用方法。
- 細胞増殖抑制又は細胞毒抑制として使用するための、請求項1乃至4のいずれかに記載のクラスター(AQCs)。
- ガン治療用薬剤を調製するために請求項1乃至4のいずれか1項に記載のクラスター(AQCs)を使用するクラスターの使用方法。
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JP2003342605A (ja) | 2002-05-21 | 2003-12-03 | Akio Komatsu | 超微粒子、超微粒子結晶膜及び超微粒子結晶の製造方法 |
JP2004107728A (ja) | 2002-09-18 | 2004-04-08 | Ebara Corp | 接合材料及び接合方法 |
JP2004292947A (ja) | 2003-03-05 | 2004-10-21 | Fuji Photo Film Co Ltd | 磁性粒子の製造方法及び磁性粒子並びに磁気記録媒体 |
JP2005199267A (ja) | 2003-12-15 | 2005-07-28 | Nippon Sheet Glass Co Ltd | 金属担持体の製造方法及び金属担持体 |
WO2005082561A1 (ja) | 2004-02-27 | 2005-09-09 | Sanc Salaam Corporation | コロイダル金属 |
JP2005290498A (ja) | 2004-04-01 | 2005-10-20 | Mitsubishi Materials Corp | 低温燒結性に優れた銀粘土用銀粉末およびこの銀粉末を含む銀粘土 |
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KR101361266B1 (ko) | 2014-02-11 |
KR101424943B1 (ko) | 2014-08-01 |
ES2277531B2 (es) | 2008-07-16 |
JP2009507996A (ja) | 2009-02-26 |
JP6186103B2 (ja) | 2017-08-23 |
JP2015063759A (ja) | 2015-04-09 |
EP1914196A1 (en) | 2008-04-23 |
ES2277531A1 (es) | 2007-07-01 |
US9421610B2 (en) | 2016-08-23 |
EP1914196A4 (en) | 2010-12-29 |
WO2007017550A1 (es) | 2007-02-15 |
KR20130140212A (ko) | 2013-12-23 |
CN101248003A (zh) | 2008-08-20 |
KR20080039467A (ko) | 2008-05-07 |
US20090035852A1 (en) | 2009-02-05 |
JP2018111885A (ja) | 2018-07-19 |
EP1914196B1 (en) | 2020-05-06 |
JP6364319B2 (ja) | 2018-07-25 |
ES2799308T3 (es) | 2020-12-16 |
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