图4在不同温度下退火ZIF-8颗粒获得样品的N1s谱图和吡啶-N、博海吡咯-N和石墨-N的含量(a)在600ºC温度下退火ZIF-8颗粒获得样品的N1s谱图。
1.2.2靶向药物运输与诊疗一体化除了生物成像外,拾贝人们还致力于探索金属纳米团簇的潜在靶向诊疗应用。图6(a)Au18(SC6H11)14[12],机械(b)Au20(TBBT)16[13],机械(c)[Au23(SC6H11)16]- [14],(d)Au24(SAdm)16[15],(e)Au25(PET)18[16],(f)[N(C8H17)4][Au25(PET)18][17],(g)Au28(TBBT)20[18],(h)Au30S(S-t-Bu)18[19],(i)Au36(SPh-tBu)24[20],(j)Au38(PET)24[21],(k)Au40(o-MBT)24[22],(l)Au52(TBBT)32[22],(m)Au92(TBBT)44[23],(n)Au102(p-MBA)44[24],(o)Au130(p-MBT)50[25]和(p)Au133(SPh-tBu)52[26]纳米团簇的单晶结构图。
由于量子尺寸效应以及极高的表面-体积比,飞升金属纳米团簇表现出与等离子体对应物根本不同的性质。通常,博海金属纳米团簇的红外光谱的其他特征倾向于与相应的游离配体的那些相同,主要用于定性分析。三、拾贝金属纳米团簇的分类以上介绍了金属纳米团簇的合成方法以及相应机理,拾贝那么合成出来的金属纳米团簇种类究竟又有哪些呢?如果按纳米团簇金属核分类的话则分为金、银、铜等单金属纳米团簇或者金银,金铜等合金纳米团簇。
金属纳米团簇,机械别说遇到火了,也许温度稍微高于100摄氏度可能就坏了。例如,飞升周等人[42]在Au20(SR)16和磷化氢保护的Au20纳米团簇中发现了显著的电荷转移和溶剂化动力学。
七、博海参考文献(标红的为文章中提到的综述)[1] Yan,N.;Xia,N.;Liao,L.;Zhu,M.;Jin,F.;Jin,R.;Wu,Z.Unravelingthelong-pursuedAu144 structurebyx-raycrystallography. Sci.Adv.2018,4,DOI:10.1126/sciadv.aat7259.[2]Jin,R.;Zeng,C.;Zhou,M.;Chen,Y.AtomicallyPreciseColloidalMetalNanoclustersandNanoparticles:FundamentalsandOpportunities.Chem.Rev. 2016,116,10346-10413.[3]Yao,Q.;Chen,T.;Yuan,X.;Xie,J.TowardTotalSynthesisofThiolate-ProtectedMetalNanoclusters.Acc.Chem.Res.2018, 51,1338-1348.[4]Luo,Z.;Nachammai,V.;Zhang,B.;Yan,N.;Leong,D.T.;Jiang,D.-e.;Xie,J.TowardUnderstandingtheGrowthMechanism:TracingAllStableIntermediateSpeciesfromReductionofAu(I)-ThiolateComplexestoEvolutionofAu25 Nanoclusters.J.Am.Chem.Soc. 2014,136,10577-10580.[5]Yao,Q.;Yuan,X.;Fung,V.;Yu,Y.;Leong,D.T.;Jiang,D.-e.;Xie,J.UnderstandingSeed-MediatedGrowthofGoldNanoclustersatMolecularLevel.Nat.Commun. 2017,8,927.[6]Wang,S.;Li,Q.;Kang,X.;Zhu,M.CustomizingtheStructure,Composition,andPropertiesofAlloyNanoclustersbyMetalExchange.Acc.Chem.Res.2018, 51, 2784-2792.[7]Yao,Q.;Feng,Y.;Fung,V.;Yu,Y.;Jiang,D.-e.;Yang,J.;Xie,J.PreciseControlofAlloyingSitesofBimetallicNanoclustersviaSurfaceMotifExchangeReaction.Nat.Commun. 2017,8,1555.[8]Chakraborty,I.;Pradeep,T.AtomicallyPreciseClustersofNobleMetals:EmergingLinkbetweenAtomsandNanoparticles.Chem.Rev. 2017,117,8208-8271.[9]Negishi,Y.;Nobusada,K.;Tsukuda,T.Glutathione-ProtectedGoldClustersRevisited:BridgingtheGapbetweenGold(I)ThiolateComplexesandThiolate-ProtectedGoldNanocrystals.J.Am.Chem.Soc.2005,127,5261-5270.[10]Negishi,Y.;Chaki,N.K.;Shichibu,Y.;Whetten,R.L.;Tsukuda,T.OriginofMagicStabilityofThiolatedGoldClusters:ACaseStudyonAu25(SC6H13)18. J.Am.Chem.Soc. 2007,129, 11322-11323.[11]Dass,A.;Stevenson,A.;Dubay,G.R.;Tracy,J.B.;Murray,R.W.NanoparticleMALDI-TOFMassSpectrometrywithoutFragmentation:Au25(SCH2CH2Ph)18 andMixedMonolayerAu25(SCH2CH2Ph)18-x(L)x. J.Am.Chem.Soc. 2008,130,5940-5946.[12] Chen,S.;Wang,S.;Zhong,J.;Song,Y.;Zhang,J.;Sheng,H.;Pei,Y.;Zhu,M.TheStructureandOpticalPropertiesofthe[Au18(SR)14]Nanocluster. Angew.Chem.,Int.Ed.2015,54,3145-3149.[13] Zeng,C.;Liu,C.;Chen,Y.;Rosi,N.L.;Jin,R.Gold-ThiolateRingasaProtectingMotifintheAu20(SR)16 NanoclusterandImplications.J.Am.Chem.Soc.2014,136,11922-11925.[14] Das,A.;Li,T.;Nobusada,K.;Zeng,C.;Rosi,N.L.;Jin,R.Nonsuperatomic[Au23(SC6H11)16]- NanoclusterFeaturingBipyramidalAu15 KernelandTrimericAu3(SR)4 Motif. J.Am.Chem.Soc.2013,135,18264-18267.[15]Crasto,D.;Barcaro,G.;Stener,M.;Sementa,L.;Fortunelli,A.;Dass,A.Au24(SAdm)16 Nanomolecules:X-rayCrystalStructure,TheoreticalAnalysis,AdaptabilityofAdamantaneLigandstoFormAu23(SAdm)16 andAu25(SAdm)16,andItsRelationtoAu25(SR)18.J.Am.Chem.Soc. 2014, 136, 14933-14940.[16]Heaven,M.;Dass,A.;White,P.;Holt,K.;Murray,R.CrystalStructureoftheGoldNanoparticle[N(C8H17)4]-[Au25(SCH2CH2Ph)18].J.Am.Chem.Soc.2008,130,3754-3755.[17]Zhu,M.;Aikens,C.M.;Hollander,F.J.;Schatz,G.C.;Jin,R.CorrelatingtheCrystalStructureofAThiol-ProtectedAu25 ClusterandOpticalProperties.J.Am.Chem.Soc.2008, 130,5883-5885.[18]Zeng,C.;Li,T.;Das,A.;Rosi,N.L.;Jin,R.ChiralStructureofThiolate-Protected28-Gold-AtomNanoclusterDeterminedbyX-rayCrystallography.J.Am.Chem.Soc.2013,135,10011-10013.[19]Crasto,D.;Malola,S.;Brosofsky,G.;Dass,A.;Hakkinen,H.̈SingleCrystalXRDStructureandTheoreticalAnalysisoftheChiralAu30S(S-t-Bu)18 Cluster.J.Am.Chem.Soc.2014,136,5000-5005.[20]Zeng,C.;Qian,H.;Li,T.;Li,G.;Rosi,N.L.;Yoon,B.;Barnett,R.N.;Whetten,R.L.;Landman,U.;Jin,R.TotalStructureandElectronicPropertiesoftheGoldNanocrystalAu36(SR)24.Angew.Chem.,Int.Ed. 2012,51,13114-13118.[21]Qian,H.;Eckenhoff,W.T.;Zhu,Y.;Pintauer,T.;Jin,R.TotalStructureDeterminationofThiolate-ProtectedAu38 Nanoparticles. J.Am.Chem.Soc. 2010, 132, 8280-8281.[22]Zeng,C.;Chen,Y.;Liu,C.;Nobusada,K.;Rosi,N.L.;Jin,R.GoldTetrahedraCoilup:Kekule-likeandDoubleHelicalSuper-structures.Sci.Adv.2015,1, e1500425.[23]Zeng,C.;Liu,C.;Chen,Y.;Rosi,N.L.;Jin,R.AtomicStructureofSelf-AssembledMonolayerofThiolatesonaTetragonalAu92 Nanocrystal.J.Am.Chem.Soc.2016,138,8710-8713.[24]Jadzinsky,P.D.;Calero,G.;Ackerson,C.J.;Bushnell,D.A.;Kornberg,R.D.StructureofaThiolMonolayer-ProtectedGoldNanoparticleat1.1ÅResolution.Science2007, 318,430-433.[25]Chen,Y.;Zeng,C.;Liu,C.;Kirschbaum,K.;Gayathri,C.;Gil,R.R.;Rosi,N.L.;Jin,R.CrystalStructureofBarrel-ShapedChiralAu130(p-MBT)50 Nanocluster.J.Am.Chem.Soc.2015,137,10076-10079.[26]Dass,A.;Theivendran,S.;Nimmala,P.R.;Kumara,C.;Jupally,V.R.;Fortunelli,A.;Sementa,L.;Barcaro,G.;Zuo,X.;Noll,B.C.Au133(SPh-tBu)52 Nanomolecules:X-rayCrystallography,Optical,Electrochemical,andTheoreticalAnalysis.J.Am.Chem.Soc. 2015,137,4610-4613.[27]Wu,Z.;Jin,R.StabilityoftheTwoAu-SBindingModesinAu25(SG)18NanoclustersProbedbyNMRandOpticalSpectroscopy.ACSNano2009,3,2036-2042.[28]Cook,A.W.;Hayton,T.W.CaseStudiesinNanoclusterSynthesisandCharacterization:ChallengesandOpportunities.Acc.Chem.Res., 2018, 51,2456-2464.[29] Jin,R.Atomicallyprecisemetalnanoclusters:stablesizesandopticalproperties.Nanoscale,2015,7,1549-1565.[30]Tang,Z.;Xu,B.;Wu,B.;Robinson,D.A.;Bokossa,N.;Wang,G.MonolayerReactionsofProtectedAuNanoclusterswithMonothiolTioproninand2,3-DithiolDimercaptopropanesulfonate.Langmuir,2011,27,2989-2996.[31]Tang,Z.;Ahuja,T.;Wang,S.;Wang,G.NearInfraredLuminescenceofGoldNanoclustersAffectedbytheBondingof1,4-DithiolateDureneandMonothiolatePhenylethanethiolate.Nanoscale,2012,4,4119-4124.[32]Conroy,C.V.;Jiang,J.;Zhang,C.;Ahuja,T.;Tang,Z.;Prickett,C.A.;Yang,J.J.;Wang,G.EnhancingnearIrLuminescenceofThiolateAuNanoclustersbyThermoTreatmentsandHeterogeneousSubcellularDistributions.Nanoscale,2014,6,7416-7423.[33]Negishi,Y.;Iwai,T.;Ide,M.ContinuousModulationofElectronicStructureofStableThiolate-ProtectedAu25 ClusterbyAgDoping.Chem.Commun. 2010,46,4713-4715.[34]Wang,S.;Meng,X.;Das,A.;Li,T.;Song,Y.;Cao,T.;Zhu,X.;Zhu,M.;Jin,R.A200-FoldQuantumYieldBoostinthePhotoluminescenceofSilver-DopedAgxAu25-xNanoclusters:The13thSilverAtomMatters.Angew.Chem.,Int.Ed.2014,53,2376-2380.[35] Goswami,N.;Yao,Q.;Luo,Z.;Li,J.;Chen,T.;Xie,J. LuminescentMetalNanoclusterswithAggregation-InducedEmission. J.Phys.Chem.Lett. 2016,7,962-975.[36] Luo,Z.;Yuan,X.;Yu,Y.;Zhang,Q.;Leong,D.T.;Lee,J.Y.; Xie,J.FromAggregation-InducedEmissionofAu(I)-Thiolate ComplexestoUltrabrightAu(0)@Au(I)-ThiolateCore-ShellNanoclusters.J.Am.Chem.Soc. 2012,134,16662-16670.[37] Ramakrishna,G.;Varnavski,O.;Kim,J.;Lee,D.;Goodson,T. Quantum-SizedGoldClustersasEfficientTwo-PhotonAbsorbers.J. Am.Chem.Soc. 2008,130,5032-5033.[38] Philip,R.;Chantharasupawong,P.;Qian,H.;Jin,R.;Thomas, J.EvolutionofNonlinearOpticalProperties:FromGoldAtomic ClusterstoPlasmonicNanocrystals.NanoLett.2012,12,4661-4667.[39] Knoppe,S.;Vanbel,M.;vanCleuvenbergen,S.;Vanpraet,L.; Bürgi,T.;Verbiest,T.NonlinearOpticalPropertiesofThiolateProtectedGoldClusters.J.Phys.Chem.C2015,119,6221-6226.[40] Knoppe,S.;Hakkinen,H.;Verbiest,T.NonlinearOptical̈ PropertiesofThiolate-ProtectedGoldClusters:ATheoreticalSurvey oftheFirstHyperpolarizabilities. J.Phys.Chem.C 2015,119,27676-27682.[41] Yau,S.H.;Varnavski,O.;Goodson,T.,III.AnUltrafastLook atAuNanoclusters. Acc.Chem.Res. 2013,46,1506-1516.[42] Zhou,M.;Vdovic,S.;Long,S.R.;Zhu,M.Z.;Yan,L.Y.;Wang,Y.Y.;Niu,Y.L.;Wang,X.F.;Guo,Q.J.;Jin,R.C.;IntramolecularChargeTransferandSolvationDynamicsofThiolateProtectedAu20(SR)16 ClustersStudiedbyUltrafastMeasurement.J. Phys.Chem.A 2013,117,10294-10303.[43] ShangL,DongS,NienhausGU.Ultra-smallfluorescentmetalnanoclusters:Synthesisandbiologicalapplications.NanoToday,2011,6,401-418.[44] Tao, Y.; Li, M.; Ren, J.; Qu,X.Metalnanoclusters:novelprobesfordiagnosticandtherapeuticapplications.Chem.Soc.Rev. 2016,47,8636-8663.[45] Liu, L.; Corma, A.MetalCatalystsforHeterogeneousCatalysis:FromSingleAtomstoNanoclustersandNanoparticles. Chem.Rev. 2018,118,4981-5079. [46] Tang, Q.; Hu, G.; Fung, V.;Jiang,D. InsightsintoInterfaces,Stability,ElectronicProperties,andCatalyticActivitiesofAtomicallyPreciseMetalNanoclustersfromFirstPrinciples.Acc.Chem.Res., 2018, 51,2793-2802.[47]Pelayo,J.Jesús,ValenciaI,García,A.Patricio,etal.Chiralityinbareandligand-protectedmetalnanoclusters.Adv. Phys.,2018,3,965-998.[48] Zhang,X.-D.;Luo,Z.;Chen,J.;Shen,X.;Song,S.;Sun,Y.; Fan,S.;Fan,F.;Leong,D.T.;Xie,J.UltrasmallAu10-12(SG)10-12 NanomoleculesforHighTumorSpecificityandCancerRadiotherapy. Adv.Mater. 2014,26,4565-4568.作者水平有限,博海如有遗漏或者陈述不妥的地方,望指正批评,感激不已。
这篇综述详细介绍了金属纳米团簇经常用到的几种表征手段,拾贝当然除此之外,拾贝还包括了上面两节提到的纳米团簇的合成方法,分类以及下面即将介绍的纳米团簇的一些性质和相关应用方面。中华人民共和国恢复在联合国的合法席位,机械是大势所趋、众望所归。
2021年6月6日,飞升美国参议员乘坐军用飞机前往台湾宣布所谓的疫苗捐赠计划并在机场合影。博海所谓非人道帽子根本扣不到中国头上。
打疫情牌,拾贝憋了90天的情报溯源报告没有任何实锤,拾贝自己却稳坐疫情确诊和死亡病例数头把交椅,成为最大病毒培养皿,德特里克堡等国内外生物实验室更是疑云重重。无论是50年前妄图在联合国制造两个中国一中一台,机械还是其国内炮制所谓与台湾关系法和对台六项保证。