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1、Asmartcopper(II)-responsivebinucleargadolinium(III)complex-basedmagneticresonanceimagingcontrastagent†Yan-mengXiao,abGui-yanZhao,abXin-xiuFang,abYong-xiaZhao,abGuan-huaWang,cWeiYang*aandJing-weiXu*aAnovelGd-DO3A-typebismacrocycliccomplex,[Gd2(DO3A)2BMPN
2、A],withaCu2+-selectivebindingunitwassynthesizedasapotential“smart”copper(II)-responsivemagneticresonanceimaging(MRI)contrastagent.TherelaxivityofthecomplexwasmodulatedbythepresenceorabsenceofCu2+;intheabsenceofCu2+,thecomplexexhibitedarelativelylowrelax
3、ivityvalue(6.40mM1s1),whiletheadditionofCu2+triggeredanapproximately76%enhancementinrelaxivity(11.28mM1s1).Moreover,thisCu2+-responsivecontrastagentwashighlyselectiveinitsresponsetoCu2+overotherbiologically-relevantmetalions.Theinfluenceofsomecommon
4、biologicalanionsontheCu2+-responsivecontrastagentandtheluminescencelifetimeofthecomplexwerealsostudied.Theresultsoftheluminescencelifetimemeasurementsindicatedthattheenhancementinrelaxivitywasmainlyascribedtotheincreasednumberofinner-spherewatermolecule
5、sbindingtotheparamagneticGd3+coreupontheadditionofCu2+.Inaddition,thevisualchangeassociatedwiththesignificantlyenhancedrelaxivityduetotheadditionofCu2+wasobservedfromT1-weightedphantomimages.IntroductionCopper(II)ionisavitalmetalnutrientforthemetabolism
6、oflifeandplaysacriticalroleinvariousbiologicalprocesses.1,2Itshomeostasisiscriticalforthemetabolismanddevelopmentoflivingorganisms.3,4Ontheotherhand,thedisruptionofitshomeostasismayleadtoavarietyofphysicaldiseasesandneurologicalproblemssuchasAlzheimer's
7、disease,5MenkesandWilson'sdisease,6amyotrophiclateralsclerosis,7,8andpriondisease.9,10Therefore,theassessmentandunderstandingofthedistributionofbiologicalcopperinlivingsystemsbynoninvasiveimagingiscrucialtoprovidemoreinsightintocopperhomeostasisandbette
8、runderstandtherelationshipbetweencopperregulationanditsphysiologicalfunction.Awidevarietyoforganicuorescentdyeshavebeenexploitedfortheopticaldetectionofionsinthelastfewdecades.11–13However,opticalimagingusingorganicuorescentdyes